Thermal- and photoinitiated radical polymerization in the presence of an addition fragmentation agent

ABSTRACT

Disclosed are compositions from which radically initiated oligomers/polymers having a controlled molecular weight, low polydispersity and a vinyl or dienyl end group are prepared. Further subjects of the invention are a process for controlled radical polymerization, oligomers/polymers obtainable by said process and the use of specific addition fragmentation agents for the polymerization process. The addition fragmentation agents are new in part and these are also subject of the present invention. The addition fragmentation agents are of the formula (Ia), (Ib) or (Ic)                    
     where Y is a group which activates the double bond towards Michael addition.

The present invention relates to compositions, from which radicallyinitiated oligomers/polymers having a controlled molecular weight, lowpolydispersity and a vinyl or dienyl end group can be prepared. Furthersubjects of the invention are a process for controlled radicalpolymerization, oligomers/polymers obtainable by said process and theuse of specific addition fragmentation agents for the polymerizationprocess. The addition fragmentation agents are new in part and these arealso subject of the present invention.

Polymers of limited molecular weight, or oligomers, are useful asprecursors in the manufacture of other polymeric materials and asadditives in plastics, elastomers and surface coating compositions, aswell as being useful in their own right in many applications.

In conventional polymerization practice, the manufacture of oligomersrequires the use of an initiator which acts as free radical source andof a chain transfer agent. The chain transfer agent controls themolecular weight of the polymer molecule by reacting with thepropagating polymer chain. At least a part of the transfer agent isincorporated into the polymer and thus is consumed during the process.The incorporated residue of the chain transfer agent can lead toundesirable end-groups on the polymer. Common chain transfer agents arefor example alkanethiols, which cause an objectionable odour.

To avoid these deficiencies WO 88/04304 suggests nonionic acrylate orstyrene derivatives as chain transfer agents for controlled radicalpolymerization.

The use of addition fragmentation agents to control molecular weight isknown and a variety of compounds have already been suggested as forexample described by Colombani et al. in “Addition FragmentationProcesses in Free Radical Polymerization”, Prog. Polym. Sci., Vol. 21,439-503, 1996. However there is still a need to provide easilyaccessible compounds which are highly efficient in thermally and inphotochemically induced radical polymerization.

Y. Yagci et al. in J. Polym. Sci., Part A, Polym. Chem. Vol. 34,3621-3624 (1996) disclose the use of allyl onium salts, in particularpyridinium salts, together with radical initiators for cationicpolymerization.

Surprisingly it has been found that specific allyl or dienyl cationicsystems are highly efficient addition fragmentation agents, useful forthe control of molecular weight build up of radical polymerizations. Thechain transfer coefficient c_(x) is in many cases close to thetheoretically ideal value of 1. Polydispersity of the oligomers/polymersis generally small and in many cases below 2. The compounds are easilyaccessible thus being ideally suitable for industrial applications.

These polymerization processes will also control the physical propertiesof the resulting polymers such as viscosity, hardness, gel content,processability, clarity, high gloss, durability, and the like.

The polymerization processes and resin products of the present inventionare useful in many applications, including a variety of specialtyapplications, such as for the preparation of block copolymers which areuseful as compatibilizing agents for polymer blends, or dispersingagents for coating systems or for the preparation of narrow molecularweight resins or oligomers for use in coating technologies andthermoplastic films or as toner resins and liquid immersion developmentink resins or ink additives used for electrophotographic imagingprocesses.

One object of the present invention is a composition comprising

a) at least one ethylenically unsaturated monomer or oligomer

b) at least one radical initiator which forms a radical upon heating orupon irradiation with (UV) light from 305 nm to 450 nm and

c) a compound of formula (Ia), (Ib) or (Ic)

Y is a group which activates the double bond towards Michael addition;

X is halogen or the anion of a mono carboxylic acid from 1-12 carbonatoms, a monovalent oxo acid or complex acid;

n is 0 or 1;

R₁, R₂, R₃ are independently of each other hydrogen, unsubstitutedC₁-C₁₈alkyl, C₃-C₁₈alkyl, interrupted by at least one nitrogen or oxygenatom, C₃-C₁₈alkenyl, C₃-C₁₈alkynyl, C₇-C₉phenylalkyl, C₃-C₁₂cycloalkylor C₃-C₁₂cycloalkyl containing at least one nitrogen or oxygen atom; or

C₁-C₁₈alkyl or C₃-C₁₈alkyl interrupted by at least one nitrogen oroxygen atom, C₃-C₁₈alkenyl, C₃-C₁₈alkynyl, C₇-C₉phenylalkyl,C₃-C₁₂cycloalkyl or C₃-C₁₂cycloalkyl containing at least one nitrogen oroxygen atom, which are substituted by NO₂, halogen, amino, hydroxy,cyano, carboxy, C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkylamino,di(C₁-C₄alkyl)amino or by a group —O—C(O)—C₁-C₁₈alkyl; or

phenyl, naphthyl, which are unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, C₁-C₄alkylthio, halogen, cyano, hydroxy, carboxy,C₁-C₄alkylamino or di(C₁-C₄alkyl)amino; or

R₁ and R₂, together with the linking hetero atom, form aC₃-C₁₂heterocycloalkyl radical; or

R₁ and R₂ form a group,

 or

R₁, R₂ and R₃ form a group

Halogen is fluorine, chlorine, bromine or iodine, preferably chlorine orbromine.

The alkyl radicals in the various substituents may be linear orbranched. Examples of alkyl containing 1 to 18 carbon atoms are methyl,ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl,2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.

Alkenyl with 3 to 18 carbon atoms is a linear or branched radical as forexample propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl,3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl,n-2-octadecenyl oder n-4-octadecenyl. Preferred is alkenyl with 3 bis12, particularly preferred with 3 to 6 carbon atoms.

Alkinyl with 3 to 18 is a linear or branched radical as for examplepropinyl (—CH₂—C≡CH), 2-butinyl, 3-butinyl, n-2-octinyl, odern-2-octadecinyl. Preferred is alkinyl with 3 to 12, particularlypreferred with 3 to 6 carbon atoms.

C₃-C₁₂cycloalkyl is typically, cyclopropyl, cyclobutyl, cyclopentyl,methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl.

Cycloalkyl which is interrupted by at least one O or N atom is forexample 2-tetrahydropyran-yl, tetrahydrofurane-yl, 1,4 dioxan-yl,pyrrolidin-yl, tetrahydrothiophen-yl, pyrazolidin-yl, imidazolidin-yl,butyrolactone-yl, caprolactame-yl.

C₇-C₉phenylalkyl is for example benzyl, phenylethyl or phenylpropyl.

C₃-C₁₈alkyl interrupted by at least one O atom is for example—CH₂—CH₂—O—CH₂—CH₃, —CH₂—CH₂—O—CH₃ or —CH₂—CH₂—O—CH₂—CH₂—CH₂—O—CH₂—CH₃.It is preferably derived from polyethlene glycol. A general descriptionis —((CH₂)_(a)—O)_(b)—H/CH₃, wherein a is a number from 1 to 6 and b isa number from 2 to 10.

Y may be any substituent which facilitates Michael addition at thedouble bond. Preferably Y is CN, C(O)halogen, COOR₄, C(O)R₄, CONR₅R₆,phenyl or naphthyl which are unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, C₁-C₄alkylthio, halogen, nitro, cyano, hydroxy, carboxy,C₁-C₄alkylamino or di(C₁-C₄alkyl)amino; and R₄, R₅ and R₆ are hydrogenor C₁-C₁₈alkyl.

More preferably Y is CN, COOR₄ or phenyl which is unsubstituted orsubstituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, halogen, cyano,hydroxy, carboxy, C₁-C₄alkylamino or di(C₁-C₄alkyl)amino; and R₄ isC₁-C₄alkyl.

Most preferably Y is CN, COOCH₃, COOC₂H₅ or phenyl.

X is halogen or the anion of a mono carboxylic acid from 1-12 carbonatoms, a monovalent oxo acid or complex acid.

Examples of monocarboxylic acids with 1 to 12 carbon atoms are formicacid, acetic acid, propionic acid, phenyl acetic acid, cyclohexanecarbonic acid, mono-, di- and trichlor-acetic acid or mono-, di- andtrifluor-acetic acid. Other suitable acids are benzoic acid,chlorbenzoic acid, methanesulfonic acid, ethanesulfonic acid,benzenesulfonic acid, p-toluenesulfonic acid, chlorbenzenesulfonic acid,trifluormethanesulfonic acid, methylphosphonic acid or phenylphosphonicacid.

Preferably X is —Cl, —Br, —I, ClO₄ ⁻, CF₃SO₃ ⁻, CH₃SO₃ ⁻, HSO₄ ⁻, BF₄ ⁻,B(Phenyl)₄ ⁻, PF₆ ⁻, SbCl₆ ⁻, AsF₆ ⁻ or SbF₆ ⁻.

Further suitable anions are derived from alkyl-aryl-borates which aredisclosed for example in U.S. Pat. No. 4,772,530, GB 2307474, GB2307473, GB 2307472, EP 775706. Examples are triphenylbutylborate,triphenylhexylborate, triphenylmethylborate, dimesityl-phenyl-methyl- or-butylborate, di(bromomesityl)-phenyl-methyl- or -butylborate,tris(3-fluorphenyl)-hexylborate, tris(3-fluorphenyl)-methyl- or-butylborate, dichloromesityl-phenyl-methyl- or -butylborate,tris(dichloromesityl)-methylborate, tris(3-chlorphenyl)-hexylborate,tris(3-chlorphenyl)-methyl- or -butylborate,tris(3-bromphenyl)-hexylborate, tris(3-bromphenyl)-methyl- or-butylborate, tris(3,5-difluorphenyl)-hexylborate,dimesityl-biphenyl-butylborate, dimesityl-naphthylmethyl- or-butylborate, di(o-tolyl)-9-anthracyl-methyl- or -butylborate,dimesityl-9-phenanthryl-phenyl- or -butylborate

More preferably X is Cl⁻, Br⁻, ClO₄ ⁻, CF₃SO₃ ⁻, CH₃SO₃ ⁻, CF₃COO⁻, BF₄⁻, or PF₆ ⁻.

Most preferably X is Br⁻.

Preferably n is 0.

In a preferred embodiment R₁, R₂, R₃ are independently of each otherunsubstituted C₁-C₁₈alkyl, C₃-C₁₈alkyl interrupted by at least onenitrogen or oxygen atom, C₇-C₉phenylalkyl, C₃-C₁₂cycloalkyl orC₃-C₁₂cycloalkyl containing at least one nitrogen or oxygen atom; orC₁-C₁₈alkyl, C₃-C₁₈alkyl interrupted by at least one nitrogen or oxygenatom, C₇-C₉phenylalkyl, C₃-C₁₂cycloalkyl or C₃-C₁₂cycloalkyl containingat least one nitrogen or oxygen atom, which are substituted by NO₂,halogen, amino, hydroxy, cyano, carboxy, C₁-C₄alkoxy, C₁-C₄alkylthio,C₁-C₄alkylamino or di(C₁-C₄alkyl)amino; or

phenyl, which is unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, C₁-C₄alkylthio, halogen, cyano, hydroxy, carboxy,C₁-C₄alkylamino or di(C₁-C₄alkyl)amino; or

R₁ and R₂, together with the linking hetero atom, form aC₄-C₇heterocycloalkyl radical; or

R₁ and R₂ form a group,

or

 R₁, R₂ and R₃ form a group

More preferably R₁, R₂ and R₃ independently of each other areunsubstituted C₁-C₁₂alkyl, C₃-C₁₂alkyl interrupted by at least onenitrogen or oxygen atom, benzyl or phenyl, which is unsubstituted orsubstituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, halogen, cyano,hydroxy, carboxy.

In a preferred subgroup of compounds of formula (Ia), (Ib) or (Ic) Y isCN, C(O)halogen, COOR₄, phenyl which is unsubstituted or substituted byC₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, halogen, cyano, hydroxy,carboxy,

R₄, is C₁-C₈alkyl;

X is Br⁻, ClO₄ ⁻, CF₃SO₃ ⁻, CH₃SO₃ ⁻, CF₃COO⁻, BF₄ ⁻ or PF₆ ⁻; and

R₁, R₂ and R₃ independently of each other are unsubstituted C₁-C₁₂alkyl,C₃-C₁₂alkyl interrupted by at least one nitrogen or oxygen atom, benzylor phenyl, which is unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, C₁-C₄alkylthio, halogen, cyano, hydroxy, carboxy.

Preferred are compounds of formula (Ia).

Preferably the radical initiator b) is present in an amount of 0.01 to 5weight % based on the monomer or monomer mixture.

Preferably the compound of formula (Ia), (Ib) or (Ic) is present in anamount of 0.01 to 10 weight % based on the monomer or monomer mixture.

The ratio of radical initiator to the compound of formula (Ia), (Ib) or(Ic) is preferably 0.1 to 10, more preferably 0.1 to 5 and mostpreferably 0.1 to 1.

The polymerization reaction may be carried out using photoinitiatedradical polymerization. Photoinitiators useful in the present inventionare of any known class. In certain cases it may be of advantage to usemixtures of two or more photoinitiators. Typical classes ofphotoinitators are for example camphor quinone, benzophenone,benzophenone derivatives, acetophenone, acetophenone derivatives, forexample α-hydroxycycloalkyl phenyl ketones or2-hydroxy-2-methyl-1-phenyl-propanone, dialkoxyacetophenones, α-hydroxy-or α-amino-acetophenones, e.g.(4-methylthiobenzoyl)-1-methyl-1-morpholinoethane,(4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane,4-aroyl-1,3-dioxolanes, benzoin alkyl ethers and benzil ketals, e.g.dimethyl benzil ketal, phenylglyoxalic esters and derivatives thereof,dimeric phenylglyoxalic esters, peresters, e,g. benzophenonetetracarboxylic peresters as described for example in EP 126541,monoacyl phosphine oxides, e.g.(2,4,6-trimethylbenzoyl)diphenylphosphine oxide, bisacylphosphineoxides, bis(2,6-dimethoxy-benzoyl)-(2,4,4-trimethyl-pentyl)phosphineoxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide,bis(2,4,6-trimethylbenzoyl)-2,4-dipentoxyphenylphosphine oxide,trisacylphosphine oxides, halomethyltriazines, e.g.2-[2-(4-methoxy-phenyl)-vinyl]-4,6-bis-trichloromethyl-[1,3,5]triazine,2-(4-methoxy-phenyl)-4,6-bis-trichloromethyl-[1,3,5]triazine,2-(3,4-dimethoxy-phenyl)-4,6-bis-trichloromethyl-[1,3,5]triazine,2-methyl-4,6-bis-trichloromethyl-[1,3,5]triazine,hexaarylbisimidazole/coinitiators systems, e.g.ortho-chlorohexaphenyl-bisimidazole combined with2-mercaptobenzthiazole, ferrocenium compounds, or titanocenes, e.g.bis(cyclopentadienyl)-bis(2,6-difluoro-3-pyrryl-phenyl)titanium.

The photopolymerizable compositions generally comprise 0.05 to 15% byweight, preferably 0.1 to 5% by weight, of the photoinitiator, based onthe composition. The amount refers to the sum of all photoinitiatorsadded, if mixtures of initiators are employed.

Preferred compounds are of the α-hydroxyketone type, phosphoruscontaining photoinitiators as well as the mixture of α-hydroxyketonecompounds with phosphorous containing photoinitiators.

Preferred photoinitiators are of the formula PI

wherein

Ar is unsubstituted phenyl or phenyl substituted by halogen, CN, OH,C₁-C₁₇alkoxy, phenoxy, C₂-C₁₂alkenyl, —S—C₁-C₁₂alkyl, —S-phenyl,—SO₂—C₁-C₁₂alkyl, —SO₂-phenyl, —SO₂NH₂, —SO₂NH—C₁-C₁₂alkyl,—SO₂—N(C₁-C₁₂-alkyl)₂, —NH—C₁-C₁₂alkyl, —N(C₁-C₁₂alkyl)₂ or—NH—CO-phenyl, isocyanate or masked isocyanate, or Ar is substitutedwith C₁-C₁₂alkyl, which C₁-C₁₂alkyl is unsubstituted or substituted byhalogen, OH, CN, NH₂, COOH, isocyanate, masked isocyanate, alkenyl ormasked alkenyl, or Ar is thienyl, pyridyl, furyl, indanyl ortetrahydronaphthyl;

R₁₀₁ is C₁-C₈alkyl, which is unsubstituted or substituted by OH, CN,NH₂, —NHC₁-C₁₂alkyl, N(C₁-C₁₂alkyl)₂, NH—CO-phenyl, isocyanate or maskedisocyanate, C₂-C₁₂alkenyl, halogen, C₁-C₁₂alkoxy, COOH,—(CO)O—C₁-C₁₂alkyl, —O—(CO)—C₁-C₈alkyl or NR₁₀₃R₁₀₄, or R₁₀₁ isC₃-C₅alkenyl, cyclopentyl, cyclohexyl or phenyl-C₁-C₃alkyl;

R₁₀₂ has one of the meanings given for R₁₀₁, or is a group —CH₂CH₂R₅, orR₁₀₂ together with R₁₀₁ is C₂-C₈alkylene, C₃-C₉oxaalkylene,C₃-C₉azaalkylene, or an exomethylene cyclohexane ring, wherein theC₂-C₈alkylene, C₃-C₉oxaalkylene, C₃-C₉azaalkylene, or exomethylenecyclohexane ring is unsubstituted or substituted by OH, CN, halogen,C₁-C₁₂alkoxy, —(CO)O—C₁-C₁₂alkyl, —O—(CO)—C₁-C₈alkyl or NR₁₀₃R₁₀₄;

R₁₀₃ is C₁-C₁₂alkyl, C₂-C₄alkyl which is substituted by OH, C₁-C₈alkoxyor CN, or R₁₀₃ is C₃-C₅alkenyl, cyclohexyl, phenyl-C₁-C₃alkyl,unsubstituted phenyl or phenyl, which is substituted by Cl, C₁-C₄alkyl,OH, C₁-C₄alkoxy or —(CO)O—C₁-C₈alkyl;

R₁₀₄ is C₁-C₁₂alkyl, C₂-C₄alkyl which is substituted by OH, C₁-C₈alkoxyor CN, or R₁₀₄ is C₃-C₅alkenyl, cyclohexyl or phenyl-C₁-C₃alkyl, or R₁₀₄together with R₁₀₃ is C₄-C₅alkylene, which may be interrupted by —O— or—NR₁₀₆—, or R₁₀₄ together with R₁₀₂ is C₁-C₉alkylene, C₂-C₃oxaalkyleneor C₂-C₃azaalkylene;

R₁₀₅ is —CO—NH₂, —CO—NH—C₁-C₈alkyl, —CO—N(C₁-C₈alkyl)₂,—P(O)(O—C₁-C₈alkyl)₂ 2-pyrridyl or 2-oxo-1-pyrroldinyl; and

R₁₀₆ is C₁-C₄alkyl, —CH₂CH₂CN or —CH₂CH₂(CO)O—C₁-C₈alkyl.

C₁-C₁₇alkoxy is linear or branched and is for example C₁-C₁₂alkoxy,C₁-C₈- or C₁-C₆alkoxy, especially C₁-C₄alkoxy. Examples are methoxy,ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, iso-butyloxy,tert-butyloxy, pentyloxy, hexyloxy, heptyloxy, 2,4,4-trimethylpentyloxy,2-ethylhexyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy,tetradecyloxy, pentadecyloxy, hexadecyloxy or heptadecyloxy especiallymethoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy,iso-butyloxy, tert-butyloxy, preferably methoxy. C₁-C₁₂alkoxy,C₁-C₈alkoxy and C₁-C₄alkoxy have the same meanings as given above up tothe appropriate number of C-atoms.

C₂-C₁₂alkenyl is one or more times unsaturated and is for exampleC₂-C₈-alkenyl, C₂-C₆- or C₃-C₅-alkenyl, especially C₂-C₄-alkenyl.Examples are allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 3-butenyl,2-butenyl, 1,3-pentadienyl, 5-hexenyl, 7-octenyl, nonenyl, dodecenyl,especially allyl. C₃-C₅alkenyl has the same meanings as given above upto the appropriate number of C-atoms.

C₁-C₁₂alkyl is linear or branched and is for example C₁-C₁₀-, C₁-C₈- orC₁-C₆alkyl, especially C₁-C₄alkyl. Examples are methyl, ethyl, propyl,isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl, hexyl,heptyl, 2,4,4-trimethyl-pentyl, 2-ethylhexyl, octyl, nonyl, decyl,undecyl or dodecyl, preferably methyl or butyl. C₁-C₈alkyl andC₂-C₄alkyl have the same meanings as given above up to the appropriatenumber of C-atoms. In the terms —S—C₁-C₁₂alkyl, —SO₂—C₁-C₁₂alkyl,—COO—C₁-C₁₂alkyl, —SO₂NH—C₁-C₁₂alkyl, —SO₂—N(C₁-C₁₂-alkyl)₂,—NH—C₁-C₁₂alkyl and —N(C₁-C₁₂alkyl)₂, C₁-C₁₂alkyl has the meanings givenabove. In the groups —O—(CO)—C₁-C₈alkyl, —CO—NH—C₁-C₈alkyl,—CO—N(C₁-C₈alkyl)₂, —CH₂CH₂(CO)O—C₁-C₈alkyl and —P(O)(O—C₁-C₈alkyl)₂C₁-C₈alkyl has the same meanings as given above. If C₁-C₁₂alkyl issubstituted with halogen, there are, for example 1 to 3 or 1 or 2halogen substituents located at the alkyl.

The term “masked isocyanate” means a protected isocyanate group, namelyan isocyanate group, which is blocked by chemical groups, which underspecific reaction conditions can be removed. So, the formation of anoxime results in a masked isocyanate group. Examples are given, forexample in J. Coatings Technology, Vol. 61, No. 775 (August 1989). Theblocking/deblocking mechanism is, for example, demonstrated by thefollowing equation: R—N—(CO)—X (blocked isocyanate)⇄R—N═C═O+HX On theleft side the blocked isocyanate is not susceptible to reactions in theformulation, while on the right side the influence of temperature (>120°C.) deblocks HX and liberates the isocyanate group, which is now able totake part in further reactions, for example with crosslinkers. Suitableblocking agents HX are, for example, phenol, caprolactam, methyl ethylketoxime and diethyl malonate.

Phenyl-C₁-C₃alkyl is, for example, benzyl, phenylethyl, α-methylbenzyl,Phenylpropyl, or α,α-dimethylbenzyl, especially benzyl.

C₂-C₈alkylene is linear or branched alkylene as, for example, methylene,ethylene, propylene, 1-methylethylene, 1,1-dimethylethylene, butylene,1-methylpropylene, 2-methylpropylene, pentylene, hexylene, heptylene oroctylene, especially hexylene. C₄-C₅alkylene is linear or branched, forexample, 1,1-dimethylethylene, butylene, 1-methylpropylene,2-methylpropylene or pentylene. C₄-C₅alkylene, which may be interruptedby —O— or —NR₁₀₆—, is, for example, —CH₂CH₂—O—CH₂CH₂—,—CH₂CH₂—(NR₁₀₆)—CH₂CH₂—, —CH₂—O—CH₂CH₂CH₂—, —CH₂—(NR₁₀₆)—CH₂CH₂CH₂— or—CH₂CH₂—O—CH₂CH₂CH₂—. C₃-C₉oxaalkylene can contain, for example, 1-3 or1 or 2 O-atoms, especially 1 O-atom and means for example, —CH₂—O—CH₂—,—CH₂CH₂O—CH₂CH₂—, —CH₂—CH(CH₃)—O—CH₂CH₂CH₂— or —[CH₂CH₂O]_(y), whereiny=1-4. C₃-C₉azaalkylene can contain, for example, 1-3 or 1 or 2(NR₁₀₆)-groups, especially 1 such group and means, for example,—CH₂—(NR₁₀₆)—CH₂—, —CH₂CH₂—(NR₁₀₆)—CH₂CH₂—,—CH₂—CH(CH₃)—(NR₁₀₆)—CH₂CH₂CH₂— or —[CH₂CH₂(NR₁₀₆)]_(y) wherein y=1-4and wherein R₁₀₆ has the meanings given above.

The exomethylen cyclohexane ring has the following structure

Halogen is fluorine, chlorine, bromine and iodine, especially chlorineand bromine, preferably chlorine.

Preferably Ar in the formula I is unsubstituted phenyl or phenylsubstituted by C₁-C₁₂alkyl or phenyl substituted by C₁-C₄alkyl, which issubstituted with OH, R₁₀₁ and R₁₀₂ are C₁-C₄alkyl, or R₁₀₂ together withR₁₀₁ and the C-atom to which they are bonded, are C₂-C₈alkylene.

Suitable compounds of the formula I are

phenyl-1-hydroxycyclohexylketone (®Irgacure 184; Ciba-Geigy AG);

4-dodecylphenyl-2-hydroxy-prop-2-yl ketone;

4-isopropylphenyl-2-hydroxy-prop-2-yl ketone;

2-hydroxy-2-methyl-1-phenyl-propanone;

[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-prop-2-yl ketone;

4-methylphenyl-2-hydroxy-prop-2-yl ketone

[4-(2-carboxyethyl)-phenyl]-2-hydroxy-prop-2-yl ketone.

Especially preferred are phenyl-1-hydroxycyclohexylketone,2-hydroxy-2-methyl-1-phenyl-propanone,[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-prop-2-yl ketone and[4-(2-carboxyethyl)-phenyl]-2-hydroxy-prop-2-yl ketone. Thephotoinitators according to the formula I are known, some of thecompounds are commercially available and the art-skilled is familiarwith their preparation. The compounds and their preparation are, forexample, disclosed in U.S. Pat. Nos. 4,308,400; 4,315,807; 4,318,791;4,721,734; 4,347,111; 4,477,681; 4,861,916; 5,045,573.

Preferred is also a mixture of photoinitiators of at least one compoundof the formula I and at least one phosphorus containing photoinitator ofthe formula IIa or IIb

wherein

R₁₀₇ and R₁₀₈ independently of one another are C₁-C₁₈alkyl, cyclohexyl,cyclopentyl, phenyl, naphthyl or biphenyl, wherein the cyclohexyl,cyclopentyl, phenyl, naphthyl or biphenyl are unsubstituted orsubstituted by halogen, C₁-C₁₂alkyl and/or C₁-C₁₂alkoxy, or R₇ and R₈are a 5- or 6-membered S- or N-containing heterocyclic ring;

R₁₀₉ and R₁₁₀ independently of one another are cyclohexyl, cyclopentyl,phenyl, naphthyl or biphenyl, which residues are unsubstituted orsubstituted by halogen, C₁-C₄alkyl and/or C₁-C₄alkoxy, or R₁₀₉ and R₁₁₀are a 5- or 6-membered S- or N-containing heterocyclic ring, or R₁₀₉ andR₁₁₀ together with the P-atom to which they are bonded from a ring,which contains from 4 to 10 carbon atoms and which ring may besubstituted by 1 to 6 C₁-C₄alkyl radicals.

C₁-C₁₈Alkyl is branched or unbranched alkyl and is, for example,C₁-C₁₂-, C₁-C₁₀-, C₁-C₈- or C₁-C₆-alkyl, especially C₁-C₄alkyl. Examplesare methyl, ethyl, propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl,pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethyl-pentyl,decyl, dodecyl, tetradecyl, heptadecyl or octadecyl. C₁-C₁₂alkyl has thesame meanings as given above up to the appropriate number of C-atoms

Preferably R₁₀₈ as alkyl is C₄-C₈alkyl, for example n-butyl, tert-butyl,isobutyl, sec-butyl, n-octyl, 2,4,4-trimethylpentyl.

C₁-C₁₂alkoxy is linear or branched and is for example C₁-C₈- orC₁-C₆alkoxy, especially C₁-C₄alkoxy. Examples are methoxy, ethoxy,propoxy, isopropoxy, n-butyloxy, sec-butyloxy, iso-butyloxy,tert-butyloxy, pentyloxy, hexyloxy, heptyloxy, 2,4,4-trimethylpentyloxy,2-ethylhexyloxy, octyloxy, nonyloxy, decyloxy or dodecyloxy, especiallymethoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy,iso-butyloxy, tert-butyloxy, preferably methoxy.

Halogen is fluorine, chlorine, bromine and iodine, especially chlorineand bromine, preferably chlorine.

Naphthyl means α-naphthyl and β-naphthyl.

Substituted cyclopentyl, cyclohexyl, phenyl, naphthyl or biphenyl have,for example 1-5, 1-4, three, two or one substituents. For substitutedphenyl the substitution in 4-, 2,5-, 2-, 2,6- or 2,4,6-position ispreferred. Examples for such groups are 4-chlorophenyl,2,6-dichlorophenyl, 2,4,6-trichlorophenyl, difluorophenyl, 2-tolyl,4-tolyl, ethylphenyl, tert-butylphenyl, dodecylphenyl, 4-methoxyphenyl,2-methoxyphenyl, 2,6-dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl,2,4-dimethylphenyl, 2,4,6-trimethylphenyl, methylnaphthyl,isopropylnaphthyl, chloronaphthyl or ethoxynaphthyl. Furthermore, suchgroups are, for example, methoxyethylphenyl, ethoxymethylphenyl.

R₁₀₉ and R₁₁₀ preferably are substituted phenyl, for example2,6-dimethoxyphenyl, 2,6-dichlorphenyl, 2,4,6-trimethylphenyl,especially 2,4,6-trimethylphenyl. A 5- or 6-membered S- or N-containingheterocyclic ring is, for example, thienyl, pyrryl, pyrazolyl,thiazolyl, pyridyl or 1,3-, 1,2- or 1,4-diazyl, preferably thienyl orpyrryl.

If R₁₀₉ and R₁₁₀ together with the P-atom to which they are bonded forma ring containing 4 to 10 C-atoms this ring is monocyclic, bicyclic ortricyclic. A monocyclic ring formed by R₁₀₉ and R₁₁₀ together with theP-atom is preferably a phosphacyclopentane ring. A bicyclic ring formedby R₁₀₉ and R₁₁₀ together with the P-atom is preferably aphosphabicyclohexane or phosphabicyclononane ring. A tricyclic ringformed by R₁₀₉ and R₁₁₀ together with the P atom is preferably a(6H)-dibenzo[c,e][1,2]oxaphosphorine ring.

R₁₀₉ and R₁₁₀ are preferably 2,6-dimethoxyphenyl, 2,6-dimethylphenyl,2,6-dichlorophenyl or especially 2,4,6-trimethylphenyl.

R₁₀₇ and R₁₀₈ preferably are C₁-C₁₈alkyl, cyclohexyl, cyclopentyl,phenyl or phenyl substituted with C₁-C₄alkyl. Specifically preferredR₁₀₇ and R₁₀₈ are n-butyl, tert-butyl, isobutyl, sec-butyl, n-octyl,2,4,4-trimethylpentyl, phenyl or 2,5-dimethylphenyl.

The photoinitators according to the formulae IIa and IIb are known, someare commercially available compounds and the art-skilled is familiarwith their preparation. The compounds and their preparation are, forexample, disclosed in U.S. Pat. Nos. 4,792,632; 4,737,593; 4,298,738;5,218,009; 5,399,770; 5,472,992.

Suitable compounds of the formula IIa and IIb are

2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide;

bis(2,4,6-trimethylbenzoyl)-2,4-di(3-methyl-but-1-oxy)phenyl-hosphineoxide;

bis(2,4,6-trimethylbenzoyl)-2,4-dipentoxyphenyl-phosphine oxide;

bis(2,4,6-trimethylbenzoyl)-2-methyl-prop-1-yl-phosphine oxide;

bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpent-1-yl-phosphine oxide;

bis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide;

Examples for photoinitiator mixtures suitable for the instant processesare

a mixture ofbis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpent-1-yl-phosphine oxide with2-hydroxy-2-methyl-1-phenyl-propanone;

a mixture of 2-hydroxy-2-methyl-1-phenyl-propanone with(2,4,6-trimethylbenzoyl)-diphenyl phosphine oxide;

a mixture of phenyl-1-hydroxycyclohexylketone withbis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpent-1-yl-phosphine oxide;

a mixture of phenyl-1-hydroxycyclohexylketone withbis(2,4,6-trimethylbenzoyl)-2-methyl-prop-1-yl-phosphine oxide;

a mixture of phenyl-1-hydroxycyclohexylketone withbis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide;

a mixture of phenyl-1-hydroxycyclohexylketone withbis(2,4,6-trimethylbenzoyl)-2,4-dipentoxyphenyl-phosphine oxide;

a mixture of 2-hydroxy-2-methyl-1-phenyl-propanone withbis(2,4,6-trimethylbenzoyl)-2-methyl-prop-1-yl-phosphine oxide;

a mixture of 2-hydroxy-2-methyl-1-phenyl-propanone withbis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide;

a mixture of 2-hydroxy-2-methyl-1-phenyl-propanone withbis(2,4,6-trimethylbenzoyl)-2,4-dipentoxyphenyl-phosphine oxide.

The range of the α-hydroxyketone photoinitiator, compounds of theformula PI respectively, in the mixtures of these compounds withphosphorus containing photoinitiators, compounds of the formula IIa orIIb respectively, is, for example 50-95% by weight. Preferably theamount of the compounds of the formula I in the mixture is 50-75%,especially 75% (based on 100% by weight of the total mixture).

Of interest is a process, wherein the formula PI Ar is unsubstitutedphenyl or phenyl substituted by C₁-C₁₂alkyl, which C₁-C₁₂alkyl isunsubstituted or substituted by OH or COOH, R₁₀₁ and R₁₀₂ areC₁-C₁₈alkyl or R₁₀₁ together with R₁₀₂ is C₂-C₈alkylene, and wherein theformula IIa or the formula IIb R₁₀₇ and R₁₀₈ independently of oneanother are C₁-C₁₂alkyl or phenyl, wherein the phenyl is unsubstitutedor substituted by C₁-C₈alkyl and/or C₁-C₈alkoxy and R₁₀₉ and R₁₁₀independently of one another are phenyl, which is substituted byhalogen, C₁-C₄alkyl and/or C₁-C₄alkoxy.

Preferred is, for example, a mixture of2-hydroxy-2methyl-1-phenyl-propanone withbis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpent-1-yl-phosphine oxide.Especially preferred is the above mixture with an amount of2-hydroxy-2methyl-1-phenyl-propanone of 75% by weight.

Also preferred, for example, is a mixture of2-hydroxy-2methyl-1-phenyl-propanone with2,4,6-trimethylbenzoyl-phenyl-phosphine oxide. Especially preferred isthe above mixture with an amount of 2-hydroxy-2methyl-1-phenyl-propanoneof 50% by weight.

The composition to be (co)polymerized in the instant process expedientlycontains the photoinitiator of the formula PI, IIa or IIb, or thephotoinitiator mixture of the compounds of the formulae I and IIa or IIbin an amount of from 0.1 to 15% by weight, preferably from 0.2 to 5% byweight, based on the total solids content.

Additional coinitiators or sensitizers may be used. These are typicallydyes which react by energy transfer or electron transfer and suchenhance the overall quantum yield. Typical dyes are for exampletriarylmethane, such as malachit green, indoline, thiazine, such asmethylen blue, xanthone, thioxanthone, oxazine, acridine or phenazine,such as safranine, or rhodamine of formula

wherein R is alkyl or aryl and R′ is hydrogen, alkyl or aryl. Examplesare Rhodamin B, Rhodamin 6G oder Violamin R, Sulforhodamin B orSulforhodamin G.

Preferred are thioxanthone, oxazine, acridine, phenazine or rhodamine.The polymerization reaction may also be carried out using thermallyinitiated radical polymerization. The source of radicals may be abis-azo compound, a peroxide or a hydroperoxide.

Most preferably, the source of radicals is 2,2′-azobisisobutyronitrile,2,2′-azobis(2-methylbutyronitrile),2,2′-azobis(2,4-dimethylvaleronitrile),2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile),1,1′-azobis(-cyclohexanecarbonitrile),2,2′-azobis(isobutyramide)dihydrate,2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile,dimethyl-2,2′-azobisisobutyrate, 2-(carbamoylazo)isobutyronitrile,2,2′-azobis(2,4,4-trimethylpentane), 2,2′-azobis(2-methylpropane),2,2′-azobis(N,N′-dimethyleneisobutyramidine), free base orhydrochloride, 2,2′-azobis(2-amidinopropane), free base orhydrochloride,2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} or2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide.Preferred peroxides and hydroperoxides are acetyl cyclohexane sulphonylperoxide, diisopropyl peroxy dicarbonate, t-amyl perneodecanoate,t-butyl perneodecanoate, t-butyl perpivalate, t-amylperpivalate,bis(2,4-dichlorobenzoyl)peroxide, diisononanoyl peroxide, didecanoylperoxide, dioctanoyl peroxide, dilauroyl peroxide, bis(2-methylbenzoyl)peroxide, disuccinic acid peroxide, diacetyl peroxide,dibenzoyl peroxide, t-butyl per 2-ethylhexanoate,bis-(4-chlorobenzoyl)-peroxide, t-butyl perisobutyrate, t-butylpermaleinate, 1,1-bis(t-butylperoxy)3,5,5-trimethylcyclohexane,1,1-bis(t-butylperoxy)cyclohexane, t-butyl peroxy isopropyl carbonate,t-butyl perisononaoate, 2,5-dimethylhexane 2,5-dibenzoate, t-butylperacetate, t-amyl perbenzoate, t-butyl perbenzoate,2,2-bis(t-butylperoxy)butane, 2,2bis (t-butylperoxy)propane, dicumylperoxide, 2,5-dimethylhexane-2,5-di-t-butylperocide, 3-t-butylperoxy3-phenylphthalide, di-t-amyl peroxide, α,α′-bis(t-butylperoxyisopropyl)benzene, 3,5-bis(t-butylperoxy)3,5-dimethyl 1,2-dioxolane,di-t-butyl peroxide, 2,5-dimethylhexyne-2,5-di-t-butylperoxide,3,3,6,6,9,9-hexamethyl 1,2,4,5-tetraoxa cyclononane, p-menthanehydroperoxide, pinane hydroperoxide, diisopropylbenzenemono-α-hydroperoxide, cumene hydroperoxide or t-butyl hydroperoxide.

These compounds are commercially available.

Typically the ethylenically unsaturated monomer or oligomer is selectedfrom the group consisting of ethylene, propylene, n-butylene,i-butylene, styrene, substituted styrene, conjugated dienes, acrolein,vinyl acetate, vinylpyrrolidone, vinylimidazole, maleic anhydride,(alkyl)acrylic acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylicesters, (meth)acrylonitriles, (alkyl)acrylamides, vinyl halides orvinylidene halides. Preferred ethylenically unsaturated monomers areethylene, propylene, n-butylene, i-butylene, isoprene, 1,3-butadiene,α-C₅-C₁₈alkene, styrene, α-methyl styrene , p-methyl styrene or acompound of formula CH₂═C(R_(a))—(C═Z)—R_(b), where in R_(a) is hydrogenor C₁-C₄alkyl, R_(b) is NH₂, O⁻(Me⁺), glycidyl, unsubstitutedC₁-C₁₈alkoxy, C₂-C₁₀₀alkoxy interrupted by at least one N and/or O atom,or hydroxy-substituted C₁-C₁₈alkoxy, unsubstituted C₁-C₁₈alkylamino,di(C₁-C₁₈alkyl)amino, hydroxy-substituted C₁-C₁₈alkylamino orhydroxy-substituted di(C₁-C₁₈alkyl)amino, —O—CH₂—CH₂—N(CH₃)₂ or—O—CH₂—CH₂—N⁺H(CH₃)₂An⁻; An⁻ is a anion of a monovalent organic orinorganic acid; Me is a monovalent metal atom or the ammonium ion. Z isoxygen or sulfur.

Examples for R_(a) as C₂-C₁₀₀alkoxy interrupted by at least one O atomare of formula

wherein R_(c) is C₁-C₂₅alkyl, phenyl or phenyl substituted byC₁-C₁₈alkyl, R_(d) is hydrogen or methyl and v is a number from 1 to 50.These monomers are for example derived from non ionic surfactants byacrylation of the corresponding alkoxylated alcohols or phenols. Therepeating units may be derived from ethylene oxide, propylene oxide ormixtures of both.

Further examples of suitable acrylate or methacrylate monomers are givenbelow.

An- or

An⁻, wherein An⁻ and R_(a) have the meaning as defined above and R_(e)is methyl or benzyl. An⁻ is preferably Cl⁻, Br⁻ or ⁻O₃S—CH₃.

Further acrylate monomers are

Examples for suitable monomers other than acrylates are

Preferably R_(a) is hydrogen or methyl, R_(b) is NH₂, gycidyl,unsubstituted or with hydroxy substituted C₁-C₄alkoxy, unsubstitutedC₁-C₄alkylamino, di(C₁-C₄alkyl)amino, hydroxy-substitutedC₁-C₄alkylamino or hydroxy-substituted di(C₁-C₄alkyl)amino; and Z isoxygen.

Particularly preferred ethylenically unsaturated monomers are styrene,methylacrylate, ethylacrylate, butylacrylate, isobutylacrylate, tert.butylacrylate, hydroxyethylacrylate, hydroxypropylacrylate,dimethylaminoethylacrylate, glycidylacrylates, methyl(meth)acrylate,ethyl(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate,glycidyl(meth)acrylates, acrylonitrile, acrylamide, methacrylamide ordimethylaminopropyl-methacrylamide.

Another subject of the present invention is a process for preparing anoligomer, a cooligomer, a polymer or a copolymer (block or random) byfree radical polymerization of

a) at least one ethylenically unsaturated monomer or oligomer, whichcomprises (co)polymerizing the monomer or monomers/oligomers in thepresence of

b) a radical initiator which forms a radical upon heating or uponirradiation with (UV) light from 305 nm to 450 nm and

c) a compound of formula (Ia), (Ib) or (Ic) according to claim 1 bysubjecting the mixture to heat or electromagnetic radiation in thewavelength range from 305 nm to 450 nm.

Definitions and preferences for the different substituents have alreadybeen given and apply also for the polymerization process.

Preferably the radical initiator b) is present in an amount of 0.01 to 5weight % based on the monomer or monomer mixture.

Preferably the compound of formula (Ia), (Ib) or (Ic) is present in anamount of 0.01 to 10 weight % based on the monomer or monomer mixture.

The ratio of radical initiator to the compound of formula (Ia), (Ib) or(Ic) is preferably 0.1 to 10, more preferably 0.1 to 5 and mostpreferably 0.1 to 1.

The process may be carried out in the presence of an organic solvent orin the presence of water or in mixtures of organic solvents and water.Additional cosolvents or surfactants, such as glycols or ammonium saltsof fatty acids, may be present. Other suitable cosolvents are describedhereinafter.

Preferred processes use as little solvents as possible. In the reactionmixture it is preferred to use more than 30% by weight of monomer andinitiator, particularly preferably more than 50% and most preferrablymore than 80%. In many cases it is possible to polymerize without anysolvent, particularly if the process is carried out by photo initiatedradical polymerization.

If organic solvents are used, suitable solvents or mixtures of solventsare typically pure alkanes (hexane, heptane, octane, isooctane),hydrocarbons (benzene, toluene, xylene), halogenated hydrocarbons(chlorobenzene), alkanols (methanol, ethanol, ethylene glycol, ethyleneglycol monomethyl ether), esters (ethyl acetate, propyl, butyl or hexylacetate) and ethers (diethyl ether, dibutyl ether, ethylene glycoldimethyl ether), or mixtures thereof.

Aqueous polymerization reactions can be supplemented with awater-miscible or hydrophilic cosolvent to help ensure that the reactionmixture remains a homogeneous single phase throughout the monomerconversion. Any water-soluble or water-miscible cosolvent may be used,as long as the aqueous solvent medium is effective in providing asolvent system which prevents precipitation or phase separation of thereactants or polymer products until after all polymerization reactionshave been completed. Exemplary cosolvents useful in the presentinvention may be selected from the group consisting of aliphaticalcohols, glycols, ethers, glycol ethers, pyrrolidines, N-alkylpyrrolidinones, N-alkyl pyrrolidones, polyethylene glycols,polypropylene glycols, amides, carboxylic acids and salts thereof,esters, organosulfides, sulfoxides, sulfones, alcohol derivatives,hydroxyether derivatives such as butyl carbitol or cellosolve, aminoalcohols, ketones, and the like, as well as derivatives thereof andmixtures thereof. Specific examples include methanol, ethanol, propanol,dioxane, ethylene glycol, propylene glycol, diethylene glycol, glycerol,dipropylene glycol, tetrahydrofuran, and other water-soluble orwater-miscible materials, and mixtures thereof. When mixtures of waterand water-soluble or water-miscible organic liquids are selected as theaqueous reaction media, the water to cosolvent weight ratio is typicallyin the range of about 100:0 to about 10:90.

The oligomers/polymers prepared with the instant process can be used forvarious purposes, for example for the production of printing inks,varnishes, white paints, coating compositions, inter alia for paper,wood, metal or plastic, for the production of coloured pigmented paints,daylight-curable coatings for buildings and road markings, for thepreparation of clear or pigmented aqueous dispersions, for theproduction of printing plates, for the production of masks for screenprinting, as dental filling materials, for the production of adhesives,of etch or permanent resists and of solder stop masks for printedelectronic circuits, for the production of three-dimensional articles bybulk curing (UV curing in transparent moulds) or for the production offormulations used in the stereolithography process, as described, forexample, in U.S. Pat. No. 4,575,330, for the preparation of compositematerials (for example styrenic polyesters, which may contain glassfibres and other assistants) and other thick-layer compositions, for theproduction of coatings for encapsulation of electronic parts or for theproduction of coatings for optical fibres.

A further subject of the present invention is a polymer or copolymerprepared by the above process containing a vinyl- or 1,3 dienyl group atone end of the molecule. Preferably the polymers have an average numbermolecular weight (Mn) of 1000-500 000 more preferably 5000-300 000, andmost preferably 5000-100 000.

The polydispersity (PD) as defined by Mn/Mw is preferably below 3, morepreferably from 1.1 to 2.5 and most preferably from 1.1 to 2.

The chain transfer coefficient c_(x) is preferably from 0.4 to 1, morepreferably from 0.6 to 1 and most preferably from 0.7 to 1.

The thermally initiated reaction may be carried out in any vesselsuitable for radical polymerization reactions. Examples are known in theart.

Preferably the reaction temperature is kept between 60° C. and 120° C.Reaction time may vary, depending on the molecular weight desired.Typical reaction times are from 1 hour to 24 hours.

Photochemically initiated radical polymerization may be carried out forexample in an apparatus as described in WO 98/37105.

The photoreactor used to prepare the examples is fabricated in Rodoxal,an aluminum alloy, but suitable reactors can also be constructed, forexample in stainless steel or in any material compatible with themonomers employed, as for example teflon, brown glass etc. The reactorpossesses a glass window allowing transmission of the UV-light. Theoverall irradiation surface of the reactor is 26 cm² and the cellthickness is 1 cm. In this connection the “overall irradiation surface”of the reactor means the surface of the irradiated part of the reactor,namely the window and the “cell thickness” is the thickness of theinternal path (diameter) of the reactor at the irradiated part. Theprocess can also be carried out using an optical bench and a UV-cell forabsorption spectra fitted with a septum to allow reactions under argonand a magnetic stirrer. This UV-cell, similar to those used to measureUV-spectra, may be irradiated through a 2 cm² window with homogeneouslight from a Philips 100 W medium pressure mercury lamp and the coolingmay be effected through the side walls of the cell. Bigger reactordimensions, as for example an overall irradiation surface (window size)of 26 cm² with a cell thickness (diameter) of 1 cm need lamps of higheroutput and bigger. irradiation surfaces such as, for example, FusionCuring lamps F200 to F600. As those commercially available lamps have abulb length of 6 inches (about 15.5 cm; F200 lamp) or 10 inches (about25 cm; F600 lamp), the reactor should not exceed this height. Theirradiation surface can thus be adapted to the necessary reactionconditions. Naturally, for the instant process it is also possible toemploy reactors with other dimensions. The crucial point is to guaranteea controlable and homogenic generation of radicals of the photoinitiatorthroughout the reactor, which is achieved, by controling the flow of themixture and the distribution of radicals in the mixture by stirring andappropriate irradiation. This is not dependent on the size of thereactor or the irradiation surface.

The reaction time depends on the intensity of the UV-lamp, the area ofirradiation, monomer and initiator concentration and may thus vary in avery wide range, depending on the conditions actually used.

The reaction temperature of the photochemically induced polymerizationis preferably kept between 20° and 70° C. The reaction time ispreferably from 5 minutes to 5 hours, more preferably from 10 minutes to2 hours.

A further subject of the present invention is the use of a compound offormulae (Ia), (Ib) or (Ic) according to claim 1 in a radical initiatedpolymerization process.

Yet another subject of the invention are new compounds according toformula (Xa), (Xb) or (Xc)

wherein

Y is CN, C(O)halogen, COOR₄, C(O)R₄, CONR₅R₆, phenyl or naphthyl whichare unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy,C₁-C₄alkylthio, halogen, nitro, cyano, hydroxy, carboxy, C₁-C₄alkylaminoor di(C₁-C₄alkyl)amino; and

R₄, R₅ and R₆ are hydrogen or C₁-C₁₈alkyl;

X is Cl⁻, Br⁻, —I⁻, ClO₄ ⁻, CF₃SO₃ ⁻, CH₃SO₃ ⁻, CF₃COO⁻, p-toluenesulfonate, HSO₄ ⁻, BF₄ ⁻, PF₆ ⁻, SbCl₆ ⁻, AsF₆ ⁻, SbF₆ ⁻ or a monocarboxylic acid from 1-12 carbon atoms;

n is 0 or 1;

R₁, R₂ R₃ are independently of each other hydrogen, unsubstitutedC₁-C₁₈alkyl, C₃-C₁₈alkyl, interrupted by at least one nitrogen or oxygenatom, C₃-C₁₈alkenyl, C₃-C₁₈alkynyl, C₇-C₉phenylalkyl, C₃-C₁₂cycloalkylor C₃-C₁₂cycloalkyl containing at least one nitrogen or oxygen atom; or

C₃-C₁₈alkyl, C₃-C₁₈alkyl, interrupted by at least one nitrogen or oxygenatom, C₃-C₁₈alkenyl, C₃-C₁₈alkynyl, C₇-C₉phenylalkyl, C₃-C₁₂cycloalkylor C₃-C₁₂cycloalkyl containing at least one nitrogen or oxygen atom,which are substituted by NO₂, halogen, amino, hydroxy, cyano, carboxy,C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkylamino, di(C₁-C₄alkyl)amino or bya group —O—C(O)—C₁-C₁₈alkyl; or

phenyl, naphthyl, which are unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, C₁-C₄alkylthio, halogen, cyano, hydroxy, carboxy,C₁-C₄alkylamino or di(C₁-C₄alkyl)amino; or

R₁ and R₂, together with the linking hetero atom, form a C₃-C₁₂heterocycloalkyl radical; or

R₁ and R₂ form a group,

 or

R₁, R₂ and R₃ form a group

R₁₀ and R₂₀ are independently of each other C₃-C₁₈alkyl which isunsubstituted or substituted by NO₂, halogen, amino, hydroxy, cyano,carboxy, C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkylamino ordi(C₁-C₄alkyl)amino; and

R₃₀ is hydrogen or methyl.

Preferred are compounds of formula (Xa), wherein Y is phenyl, CN orCOOR₄ and R₄ is C₁-C₄alkyl.

Preferably in the compounds of formula (Xa) X is Cl or Br.

Preferably in the compounds of formula (Xa) R₂ and R₃ are C₆-C₁₂alkyl.

The compounds of formula (Ia), (Ib), (Ic), X(a), X(b) and X(c) can beprepared according to known methods.

An analogous synthesis is for example described in U.S. Pat. No.4,247,700 as well as in CA: 96 163229c. The synthesis of the acrylic andacrylonitrile derivatives is effected by Mannich reaction of thealiphatic amine with cyanacetic acid or monoesters of malonic acid inthe presence of formaldehyde solutions in water, followed by reactionwith an alkylating agent. The styrene equivalent is best synthesized inanalogy to WO88/04304 starting from α-brommethyl styrene and thecorresponding amine. Another possibility is described by in Melikyan etal. in Chemistry Papers 46 (4), 269-271 (1992) starting from thecorresponding cinnamates.

The following examples illustrate the invention.

A) PREPARATION OF COMPOUNDS Ammonium Salts with Y=CN EXAMPLE A1Preparation of 2-N,N-Dioctyl-aminomethyl 2-Acrylonitrile, Compound 101

The title compound is prepared according to EP-A-31584. 8.5 g (0.1 mol)cyano acetic acid and 24.15 g (0.1 mol) dioctylamine are dissolved in150 ml dioxane and the mixture is cooled to 10° C. 50 ml of a 36%formaldehyde solution in water are added within 15 min under stirringand stirring is continued for another 15 min. Subsequently 150 ml of a36% formaldehyde solution is added within 30 min at a temperature of12-15° C. The solution is heated to room temperature and stirred for 3h, followed by 2 h at 60° C. After cooling to room temperature thesolvent is removed and the title compound is obtained in 100% yield.Elemental analysis % calculated C, H, N: 78.4, 12.5, 9.1; % found: 78.0,12.2, 9.1.

EXAMPLE A2 2-N,N,N-Dioctylmethyl-ammoniummethyl-2-acrylonitrile,Compound 102

17.1 g of the compound of example A1 (55 mmol) are dissolved in 600 mldry CH₂Cl₂ under argon atmosphere. 7.5 g (50.7 mmol) trimethyloxoniumtetrafluoroborate are added in portions within 20 min under argonatmosphere. The mixture is stirred over night at room temperature andthe solvent is evaporated. The raw product is dissolved in 200 ml ether,washed 3 times with 250 ml water, the organic phase is dried over MgSO₄and the solvent is removed. 18.3 g (80%) of a brown oil are obtained.Elemental analysis % calculated C, H, N: 61.8, 10.1, 6.9; found: 61.3,10.0, 6.7.

EXAMPLE A3 Preparation of 2-N,N-Dioctyl-ammoniummethyl-2-acrylonitrile,Compound 103

14 g (45.6 mmol) of the compound of example A1 are dissolved in 50 mlwater and 50 ml methanol (yellow suspension). 4.5 g of a 35% HClsolution in water are added and the mixture is poured to a solution of10.02 g sodium tetrafluoroborate in 100 ml water. The title product isisolated as described in example A2. 13.1 g (73%) are obtained.

NMR (CDCl₃): 0.85 ppm (t, 6H), 1.24 ppm (m, 6H) 1.69 ppm (m, 4H), 3.03ppm (m, 4H), 3.85 ppm (s, 2H), 6.42 and 6.51 ppm (2s, 2H, olefinic).

EXAMPLE A4 Preparation of 2-N,N-Dimethyl-aminomethyl 2-Acrylonitrile,Compound 104

The title compound is prepared in analogy to example A1. Yield 70% of aslightly brown oil. Elemental analysis % calculated C, H, N: 61.2, 10.3,28.5; % found: 63.0, 9.2, 25.3.

EXAMPLE A5 Preparation of 2-N,N-Dimethyl-ammoniummethyl 2-Acrylonitrile,Compound 105

The title compound is prepared starting from the compound of example A4in analogy to example A2. Yield 39.6% white solid.

Elemental analysis % calculated C, H, N: 39.7, 6.2, 13.2; % found: 39.8,6.2, 13.1.

Ammonium Salts with Y=COOEt EXAMPLE A6 Preparation of2-N,N-Dimethyl-aminomethyl 2-Acrylocarboxyethyl, Compound 106

Compound 106 is prepared in analogy to compound 101. Yield 99%.Elemental analysis % calculated C, H, N: 61.1, 9.6, 8.9; % found: 60.7,9.5, 9.3.

EXAMPLE A7 Preparation of 2-N,N-Dioctyl-aminomethyl2-Acrylocarboxyethyl, Compound 107

Compound 107 is prepared in analogy to compound 106. Yield 99%.Elemental analysis % calculated C, H, N: 74.7, 12.3, 4.0; % found: 74.6,12.4, 9.3.

EXAMPLE A8 Preparation of Compound 108

20 g N,N-Dioctylmethylamine (78.3 mmol) in 100 ml methylethyl ketone(MEK) are heated to 60° C. under nitrogen atmosphere. 15.1 g (78.3 mmol)α-bromomethyl ethylacrylate are dropwise added. After 4 h stirring thesolvent is removed and 99% product is obtained. Elemental analysis %calculated C, H, N: 61.59, 10.34, 3.12; % found: 61.02, 10.34, 2.94.

EXAMPLE A9 Preparation of Compound 109

15.7 g compound 108 in 400 ml water and 400 ml methanol are dropped intoa solution of 12.9 g KPF₆ in 400 ml water. The slightly yellow mixtureis concentrated, 50 ml ether are added, the organic phase is separatedand washed with 50 ml water. After drying over MgSO₄ and evaporation ofsolvent a yellow wax is obtained. Yield 13.5 g (75%). Elemental analysis% calculated C, H, N: 53.79, 9.03, 2.73; % found: 53.61, 9.17, 2.76.

EXAMPLE A10 Preparation of Compound 110

8 g of compound 107 in 250 ml CH₂Cl₂ are mixed with 3.04 gtrimethyloxonium tetrafluoroborate in two portions. After stirring for12 h the title compound is isolated in 93% yield. Elemental analysis %calculated C, H, N: 60.66, 10.18, 3.08; % found: 61.08, 10.38, 3.16.

EXAMPLE A11 Preparation of Compound 111

7.7 g of compound 107 in 30 ml water are mixed with 3.5 ml HBF₄ (50%solution in water). After one hour stirring at room temperature themixture is extracted two times with ether and the organic phase iswashed with water and dried over MgSO₄. After evaporation of the solvent4.8 g of an orange oil are obtained (54.5% yield). Elemental analysis %calculated C, H, N: 59.86, 10.05, 3.17; % found: 59.90, 10.05, 3.23.

EXAMPLE A12 Preparation of Compound 112

Compound 112 is prepared in analogy to compound 111, using KPF₆.Elemental analysis % calculated C, H, N: 52.90, 8.88, 2.80; % found:53.08, 8.83, 2.83.

EXAMPLE A13 Preparation of Compound 113

6.1 g (38.8 mmol) of compound 106, 13.3 g benzyl bromide (77.6 mmol) in75 ml methyl ethyl ketone (MEK) are stirred for 2 h at 60° C. Theresulting mixture is poured into 400 ml ether, filtrated and dried. 9.96g, 78% yield of the title compound are obtained.

NMR (CDCl₃): 1.29 ppm (t, 3H), 3.12 ppm (s, 6H), 4.21 ppm (q, 2H), 4.79ppm (s, 2H), 5.04 ppm (s, 2H), 6.91 and 6.92 ppm (2xs, 2H olefinic),7.43 ppm (m, 3H), 7.64 ppm (m, 2H).

EXAMPLE A14 Preparation of Compound 114

N,N-octyldimethylamine and α-bromomethyl ethylacrylate are mixed inequimolar amounts. Temperature raises up to 60° C. After cooling to roomtemperature the product is washed with ether and dried under vacuum.Yield 41%. Elemental analysis % calculated C, H, N: 54.85, 9.21, 4.00; %found: 54.55, 9.27, 3.99.

EXAMPLE A15 Preparation of Compound 115

5 g imidazole (60.9 mmol) in 40 ml MEK are heated to 60° C. 11.75 gα-bromomethyl ethyl acrylate are added over 10 min dropwise. After 3 hat 60° C. the mixture is cooled down, poured into 300 ml water andwashed three times with 150 ml ether. The title compound is obtained in74% yield.

EXAMPLE A16 Preparation of Compound 116

Before isolation of compound 115, the water phase is dropwise added to22.4 g KPF₆ in 400 ml water. The title product precipitates partiallyand is washed four times with 250 ml CH₂Cl₂. The organic phases aredried over MgSO₄ and the solvent is evaporated. 15.3 g (74%) areobtained. Elemental analysis % calculated C, H, N: 35.31, 4.44, 8.23; %found: 34.96, 4.31, 8.30.

EXAMPLE A17 Preparation of Compound 117

A solution of 7.9 g pyridine in 20 ml methyl ethyl ketone (MEK) isheated to 60° C. and 1.93 g α-bromomethyl ethylacrylate are addeddropwise in 30 min. The mixture is stirred at 60° C. for 1.5 h. Aftercooling to room temperature the mixture is poured on 200 ml water andthe organic phase is extracted two times with water. The product isobtained in 95% yield.

EXAMPLE A18 Preparation of Compound 118

2.72 g of compound 117 in 50 ml water are added to a solution of 3.68 gKPF₆ in 20 ml water. After 1 h the solution is filtered and the solidresidue is washed with water (2×50 ml). After drying under vacuum 3.19 gof a wax are obtained (95% yield).

NMR (CDCl₃): 1.05 ppm (t, 3H, COOC—CH₃), 3.97 ppm (q, 2H, COOCH₂—Me),5.25 ppm (s, 2H, allylics), 5.28 und 5.46 (2 s, olefinics), 7.85 (t, 2H,H-3 und H-5 py), 8,34 (t, H-4-py), 8.76 ppm (d, H-2 und H-6 py).

Ammonium Salts with Y=Phenyl

α-bromomethyl-styrene is prepared according to Journal of OrganicChemistry, 1957, 22 113 or Journal of American Chemical Society, 1054,76, 2705.

EXAMPLE A19 Preparation of Compound 119

20 g dioctylmethylamine in 100 ml MEK are heated to 60° C. 1 equivalentα-bromomethyl styrene is dropwise added in 10 min. The mixture isstirred 5 h at 60° C. and then cooled to room temperature. The mixtureis poured into 800 ml ether and the product precipitates. Afterfiltration 30.4 g (86%) of a solid are obtained. Elemental analysis %calculated C, H, N: 69.0, 10.2, 3.1; % found: 69.1, 10.4, 3.0.

EXAMPLE A20 Preparation of Compound 120

30.4 g of compound 119 (67.2 mmol) in 500 ml water and 500 ml methanolare added dropwise to a solution of 24.7 g Potasium hexafluorophosphatein 800 ml water. The title compound precipitates. After filtration anddrying 31.9 g (91% yield) are obtained. Elemental analysis % calculatedC, H, N: 60.3, 9.0, 2.7; % found: 60.3, 9.0, 2.6.

EXAMPLE A21 to A25 Preparation of Compounds 121, 122, 123, 124 and 125.

All compounds are prepared in analogy to compound 120 of example A20.

Potasium trifluoromethansulfonate instead of potasiumhexafluorophosphate. Elemental analysis % calculated C, H, N: 62.1, 8.9,2.7; % found: 62.5, 9.1, 2.6.

Sodium para-toluenesulfonate instead of potasium hexafluorophosphate.Elemental analysis % calculated C, H, N: 72.9, 9.8, 2.6; % found: 72.9,9.7, 2.6.

Sodium tetraphenylborate instead of potasium hexafluorophosphate.Elemental analysis % calculated C, H, N: 86.8, 9.6, 2.0; % found: 86.7,9.4, 2.0.

Sodium tetrafluoroborate instead of potasium hexafluorophosphate.Elemental analysis % calculated C, H, N: 68.0, 10.1, 3.1; % found: 67.9,10.0, 3.1.

Trifluoroacetic acid sodium salt instead of potasiumhexafluorophosphate. Elemental analysis % calculated C, H, N: 69.25,9.55, 2.88; % found: 69.15, 9.48, 2.96.

EXAMPLE A26 Preparation of Compound 126

The title compound is prepared in analogy to compound 119. Yield 91%white solid.

NMR (CDCl₃): 3.3 ppm (s, 9H), 5.04 ppm (s, 2H), 5.82 and 6.03 ppm (2s,2H, olefinic), 7.3-7.56 ppm (m, 5H, styrenic).

EXAMPLE A27 Preparation of Compound 127

To a solution of compound 126 (6.14g, 55.8 mmol) in 60 CH₂Cl₂, 7.5 gtrimethyloxonium tetrafluoroborate are added in portions. The mixture isstirred for 16 h, filtered and washed with 4 portions of water. Afterrecrystallization from 100 ml ethanol 3.4 g (30%) of a white solid areobtained. Elemental analysis % calculated C, H, N: 39.66, 6.18, 13.21; %found: 39.59, 6.11, 13.24.

EXAMPLE A28 Preparation of Compound 128

3.15 g dimethyloctylamine (20 mmol) in 20 ml MEK are heated to 60° C.4.9 g α-bromomethyl-styrene are dropwise added in 30 min. After 2 hstirring the mixture is cooled to room temperature and poured into 400ml ether. 6.72 g of a white oil are obtained (94.8%). Elemental analysis% calculated C, H, N: 64.4, 9.1, 3.95; % found: 64.12, 9.01, 3.97.

NMR (CDCl₃): 0.86 ppm (t, 3H), 1-1,35 ppm (m, 13H), 1.54 ppm (m, 2H),3.28 ppm (s, 6H), 3.3-3.4 (m, 2H), 5.05 ppm (s, 2H), 5.84 ppm (s, 1H),6.12 ppm (s, 1H), 7.36-7.57 ppm (m, 5H).

EXAMPLE A29 Preparation of Compound 129

3.8 ml N-methylpiperidine (2.51 g, 25.37 mmol) in 100 ml MEK are heatedto 60° C. 5 g α-bromomethyl-styrene are added dropwise in 5 min. After 8h the mixture is cooled to room temperature and poured into 600 mlether. After washing and drying 5.47 g (73%) of a white solid areobtained. Elemental analysis % calculated C, H, N: 60.81, 7.49, 4.72; %found: 60.68, 7.70, 4.80.

EXAMPLE A30 Preparation of Compound 130

The title compound is prepared in analogy to example A19. 14.46g (88%)of a white solid are obtained.

NMR (CDCl₃): 1.29 ppm (t, 9H), 3.32 ppm (q, 6H), 4.68 ppm (s, 2H), 5.73and 5.9 ppm (2s, 2H, olefinic), 7.32-7.45 ppm (m, 5H, styrenic).

EXAMPLE A31 Preparation of Compound 131

The title compound is prepared in analogy to example A19. Elementalanalysis % calculated C, H, N: 71.97, 10.98, 2.54; % found: 70.44,10.55, 2.37.

EXAMPLE A32 Preparation of Compound 132

108 ml of a 33% solution of dimethylamine in ethanol are diluted with250 ml MEK and heated to 60° C. 46.36 g (0.2 mol) α-bromomethylstyreneare added dropwise in 30 min. The mixture is stirred for 1 h at 60° C.and cooled down to room temperature. Solvent is evaporated, the residueredissolved in ethylacetate and purified on silica gel. 27.8 g (86%) ofa yellowish oil are obtained.

EXAMPLE A33 Preparation of Compound 133

8.6 g (50 mmol) of compound 132 in 50 ml MEK are heated to 60° C. 5.1 ml(6.8 g, 50 mmol) 4-brom-1-butene are added in 30 min. The mixture ispoured in 200 ml ether. The ether phase is removed, the residue iswashed with ether and concentrated. After drying under vacuum 11.92 g ofa resinous product are obtained (80.4%)

NMR (CDCl₃): 2.47 ppm (m, 2H, allylic), 3.25 ppm (s, 6H, CH₃), 3.44 ppm(m, 2H), 5.02 ppm (s, 2H), 5.8-4.98 ppm (3H, term. olefinic), 5.79 and6.06 (2s, 2H, olefinic), 7.3-7.54 ppm (m, 5H, styrenic).

EXAMPLE A34 Preparation of Compound 134

The title compound is prepared in analogy to compound 133 of exampleA33, with 4.7 ml (40 mmol) of 4-bromo-1-pentene and 6.45 g of compound132. Yield 31.6%. Elemental analysis % calculated C, H, N: 61.94, 7.80,4.51; % found: 61.84, 7.87, 4.43.

EXAMPLE A35 Preparation of Compound 135

The title compound is prepared in analogy to compound 133 of exampleA33.

NMR (CDCl₃): 1.17 ppm (m, 2H), 1.63 ppm (m, 2H), 1.96 ppm (m, 2H), 3.27ppm (s, 6H), 4.98 ppm (s, 2H), 4.9-5.67 ppm (m, 3H, terminal olefin),5,8 and 6.06 ppm (2s, 2H) 7.32-7.52 ppm (m, 5H, styrenic).

EXAMPLE A36 Preparation of Compound 136

The title compound is prepared in analogy to compound 133 of exampleA33, with 6.3 ml (50 mmol) 1-Bromo-3-Methyl-butane give a yield of 42.3%

NMR (CDCl₃): 0.76 ppm (d, 6H, J=6.5 Hz), 1.29-1.53 ppm (m, 3H), 3,23 ppm(s, 6H), 3.345 ppm (m, 2H), 4.98 ppm (s, 2H), 5.78 and 6.07 ppm (2s, 2H,olefinic), 7.32-7.51 ppm (m, 5H, styrenic).

EXAMPLE A37 Preparation of Compound 137

11.46 g (50 mmol) α-bromomethyl-styrene is added dropwise at 60° C. in30 min to a solution of 36.17 g N,N-dioctylamine in 200 ml MEK. Thesolution is stirred at 60° C. for 8 h and cooled down to roomtemperature. The mixture is poured in 200 ml toluene, the organic phaseis washed three times with 250 ml water dried over MgSO₄ andconcentrated. 24.1 g of the title product are obtained and used for thenext reaction step.

EXAMPLE A38 Preparation of Compound 138

12.47 g of compound 137 in 50 ml water and 100 ml methanol are treatedwith 3.11 g of a 35% HCl solution in water and a solution of 6.95 gNaBF₄ in 70 ml water is dropwise added. After 25 min methanol is removedand a brown emulsion is obtained, 100 ml ether are added and the organicphase is dried over MgSO₄. After evaporation of the solvent 9 g of anoil are obtained (57%).

NMR (CDCl₃): 0.87 ppm (t, 6H, C₈-termini), 1.22 ppm (m, 20H), 1.4 ppm(m, 4 H), 2.38 ppm (t, 4H, N⁺CH₂), 3.37 (s, 3H, N+CH₃), 5.25 und 5.39ppm (2s, 2H, olefins), 7.2-7.5 ppm (m, 5H, styrenic).

EXAMPLE A39 Preparation of Compound 139

4.83 g of compound 137 are dissolved in 100 ml water and 50 ml MeOH.1.72 ml hexafluoro acid (65% in water) are added in 10 min. The mixtureis stirred for 6 h at room temperature, several times extracted withether, the organic phase dried over MgSO₄ and the solvent evaporated.4.07 g (60%) of the title compound are obtained. Elemental analysis %calculated C, H, N: 59.65, 8.81, 2.78; % found: 59.73, 8.48, 2.76.

EXAMPLE A40 Preparation of Compound 140

5 g N-methylimidazole in 40 ml MEK are heated to 60° C. and 12 gα-bromomethyl-styrene are added in 10 min. After 2,5 h stirring, themixture is poured into 400 ml water, and extracted with ether. The waterphase is directly used for the next reaction step.

EXAMPLE A41 Preparation of Compound 141

Approximately 17 g of compound 140 in 400 ml water are slowly added to asolution of 22.4 (2 Aeq.) potasium hexafluorophosphate in 200 ml water.After 1.5 h the suspension is filtered, washed and dried. Elementalanalysis % calculated C, H, N: 45.36, 4.39, 8.14; % found: 45.57, 4.50,8.16.

EXAMPLE A42 Preparation of Compound 142

34.8 ml octylamin in 200 ml ether are heated to 40° C. and 16.04 gα-bromomethyl-styrene are added dropwise in 10 min. The mixture isstirred for 8 h at room temperature, filtered, dried andchromatographically purified. 6.36 g (37%) of the title compound areobtained. Elemental analysis % calculated C, H, N: 83.20, 11.09, 5.71; %found: 83.24, 11.29, 5.77.

EXAMPLE A43 Preparation of Compound 143

To 5 g of compound 142 in 200 ml water the equivalent amount of HBr isadded. The product is filtered off. Elemental analysis % calculated C,H, N: 62.57, 8.65, 4.29; % found: 62.67, 8.60, 4.39.

EXAMPLE A44 Preparation of Compound 144

0.75 g of compound 143 in 10 ml water and 30 ml MeOH are added to asolution of 0.5 g NaBF₄ in 10 ml water. After 1 h at room temperaturethe mixture is extracted with ether, the organic phase is washed withwater, dried over MgSO₄ and the solvent evaporated. After purificationby chromatography 200 mg product (26%) are obtained.

NMR (CDCl₃): 085 ppm (s, 3H), 1.2 ppm (broad s, 10H), 1.54 ppm (s, 2H),2.77 ppm (m, 2H), 3.94 ppm (s, 2H), 4.39 ppm (s, 2H) 5.40 and 5.55 ppm(2s, 2H, olefinic) 7.2-7.4 ppm (m, 5H, styrenic).

EXAMPLE A45 Preparation of Compound 145

3.96 g pyridine in 80 ml MEK are heated to 60° C. 11.73 gα-bromomethyl-styrene are added in 15 min and the solution stirred for 8h at 60° C. After cooling to room temperature, filtration and washingwith MEK, 85 g (42.4%) of the title compound are obtained. Elementalanalysis % calculated C, H, N: 60.89, 5.10, 5.07; % found: 60.95, 5.1,5.11.

EXAMPLE A46 Preparation of Compound 146

5.52 g of compound 145 in 100 ml water are added dropwise to a solutionof KPF₆ in 20 ml water. The solid product is filtered off, washed anddried. 3.6 g (53%) of the title compound are obtained. Elementalanalysis % calculated C, H, N: 49.28, 4.14, 4.10; % found: 49.30, 4.21,4.06.

EXAMPLE A47 Preparation of Compound 147

4.97 g diazabicyclononane and 9.17 g α-bromomethyl-styrene in 80 mltoluene are mixed and stirred for 18 h at room temperature. The solventis evaporated and the residue is extracted with ether. After evaporationof the solvent 10.9 g (85%) of the title compound are obtained.

NMR (CDCl₃): 2.05-2.23 ppm (m, 4H), 3.18 ppm (t, 2H), 3.52 ppm (m, 4H),3.81 ppm (t, 2H), 4.48 ppm (s, 2H), 5.23 and 5.49 ppm (2s, 2H, olefinic)7.29 ppm (m, 5H, styrenic).

EXAMPLE A48 Preparation of Compound 148

6.43 g of compound 147 in 150 ml water are added dropwise in 15 min to asolution of 7.53 g potasium trifluormethanesulfonate in 250 ml water.The mixture is stirred for 90 min at room temperature, extracted withethylacetate, the organic phase is washed several times with water anddried over MgSO₄. After evaporation of the solvent 3.96 g (50%) of thetitle compound are obtained. Elemental analysis % calculated C, H, N:52.30, 5.42, 7.18; % found: 51.77, 5.40, 7.21.

EXAMPLE A49 Preparation of Compound 149

1.4 g of compound 147 in 150 ml water are added to a solution of 3 gsodium tetraphenylborate in 150 ml water in 15 min. After 1 h stirringat room temperature, the mixture is extracted with CH₂Cl₂, the organicphase is washed with water and the solvent is evaporated. The solidresidue is extracted with MeOH and the solid filtered off. 1.59 g (65%)of the title compound are obtained.

NMR (CDCl₃): 1.27 ppm (m, 2H), 1.42 ppm (m, 2H), 1.83 ppm (m, 2H), 2.37ppm (m, 2H), 2.57 ppm (m, 2H), 2.8 ppm (m, 2H), 3.54 ppm (s, 2H), 4.83und 5.34 ppm (2s, 2H, olefinic), 5.81, 6.95, 7.11, 7.23, 7.32 und 7.4ppm (m, 25H, styrenic+tetraphenylborate).

EXAMPLE A50 Preparation of Compound 150

The title compound is prepared in analogy to compound 119, withdihexyl-(3-methyl-butyl)-amine. Yield 75% white solid.

¹H-NMR (300 MHz, CDCl₃): 0.75-0.85 ppm (m, 12H), 0.93-1.08 ppm (m, 4H),1.09-1.27 ppm (m, 16H), 1.30-1.42 ppm (m, 1H), 1.42-1.66 ppm (m, 6H),3.04-3.21 ppm (m, 6H), 4.78 ppm (s, 2H), 5.70 and 5.83 ppm (2s, 2H,olefinic), 7.25-7.46 (m, 5H, styrenic).

¹³C-NMR (75 MHz, CDCl₃): 14.3, 22.7, 22.8, 26.4, 26.5, 29.3, 30.8, 31.8,58.4, 59.4, 62.8, 127.1, 129.1, 129.5, 129.6, 138.5, 140.1.

EXAMPLE A51 Preparation of Compound 151

The title compound is prepared in analogy to compound 119, withtriisopentylamine. Yield 79% white solid.

¹H-NMR (300 MHz, CDCl₃): 0.85 ppm (d, J=6.6 Hz, 18H), 1.30-1.44 ppm (m,6H), 1.47-1.58 ppm (m, 6H), 3.15-3.25 ppm (m, 6H), 4.81 ppm (s, 2H),5.74 and 5.90 ppm (2s, 2H, olefinic), 7.30-7.50 ppm (m, 5H, styrenic).

¹³C-NMR (75 MHz, CDCl₃): 22.7, 26.6, 30.9, 58.6, 63.0, 127.1, 129.2,129.5, 129.8, 138.5, 140.2. ESI-TOF-MS: 344.4 ([M-Br]⁺), 769.8([2M-Br]⁺).

EXAMPLE A52 Preparation of Compound 152

The title compound is prepared in analogy to compound 119, withheptanoic acid 4-dimethylamino-1-methyl-butyl ester. Yield 77% beigesolid.

¹H-NMR (300 MHz, CDCl₃): 0.82-0.92 ppm (m, 3H), 1.17 ppm (d, J=6.3 Hz,3H), 1.21-1.85 ppm (m, 12H), 2.22-2.31 ppm (m, 2H), 3.24 ppm (s, 3H),3.27 ppm (s, 3H), 3.41-3.54 ppm (m, 2H), 4.73-4.85 ppm (m, 1 H), 5.06ppm (s, 2H), 5.85 and 6.11 ppm (2s, 2H, olefinic), 7.31-7.48 ppm (m, 3H,styrenic), 7.52-7.60 ppm (m, 2H, styrenic).

¹³C-NMR (75 MHz, CDCl₃): 14.3, 19.5, 20.4, 22.8, 25.3, 29.1, 31.7, 32.6,34.9, 51.4, 64.2, 67.0, 127.0, 129.2, 129.7, 129.9, 138.2, 139.5, 173.8.ESI-TOF-MS: 360.3 ([M-Br]⁺), 801.6 ([2M-Br]+).

EXAMPLE A53 Preparation of Compound 153

The title compound is prepared in analogy to compound 119, withdihexyl-(3-phenyl-propyl)-amine. Yield 52% white solid.

¹H-NMR (300 MHz, CDCl₃): 0.75-0.84 ppm (m, 6H), 0.92-1.23 ppm (m, 12H),1.40-1.58 (m, 4H), 1.97-2.10 ppm (m, 2H), 2.47-2.56 (m, 2H), 3.16-3.26ppm (m, 6H), 4.74 ppm (s, 2H), 5.64 and 5.77 ppm (2s, 2H, olefinic),7.08-7.42 ppm (m, 10H, styrenic).

¹³C-NMR (75 MHz, CDCl₃): 15.0, 23.5, 25.3, 26.9, 32.2, 33.1, 59.5, 60.4,63.8, 127.8, 129.7, 129.9, 130.0, 130.4, 130.6, 139.1, 140.5, 140.9.ESI-TOF-MS: 420.5 ([M-Br]⁺).

Phosphonium Salts EXAMPLE A54 Preparation of Compound 154

6.4 g tris-isopropyl phosphine (0.04 mol) are added dropwise to 7.5 g(0.04 mol) α-bromo-methyl-styrene in tetrahydrofurane (THF). The whitesolid which immediately precipitates is filtered off and dried. 13 g(100%) of the title compound are obtained. Elemental analysis %calculated C, H: 60.51, 8.46% found: 60.49, 8.56.

EXAMPLE A55 Preparation of Compound 155

6.08 g of compound 154 (17 mmol) in 50 ml water are added dropwise to asolution of 11.5 g (34 mmol) potasium-nonafluoro-1-butanesulfonate in 50ml water. The white solid which immediately precipitates is filtered offand dried. 8.05 g (82%) of the title compound are obtained. Elementalanalysis % calculated C, H,: 45.84%, 5.25% found: 45.86%, 5.22%.

EXAMPLE A56 Preparation of Compound 156

The title compound is prepared in analogy to compound 155 in 77.5%yield. Elemental analysis % calculated C, H: 63.15, 9.08 found: 63.04,8.90.

EXAMPLE A57 Preparation of Compound 157

To a solution of 6.6 g (34.1 mmol) α-bromomethyl-carboxylate in 50 mltetrahydrofurane 6.9 g tributylphosphine (34.1 mmol) are added underargon atmosphere. The title compound precipitates, is washed withtetrahydrofurane and dried. 94.1% are obtained. NMR (CDCl₃): 0.97 ppm(m, 9H), 1.34 ppm (t, 3H), 1.53 ppm (m, 12H), 2.43 ppm (m, 6H), 3.9 and3.96 ppm (2s, 2H) 4.24 ppm (q, 2H), 6.55 und 6.67 ppm (2s, 2H olefinic),6.78-6.80 ppm (2s, 2H, olefinic).

Dienes EXAMPLE A58 Preparation of Compound 158

The bromide is prepared according to Jiang S., Viehe H., Oger N. andCharmot P., Macromol. Chem. Phys. 1995, 196, 2349.

5.11 g dioctylamine (20 mmol) and 2.94 g 5-bromo-1,3-pentadiene in 30 mlmethyl ethyl ketone are heated to 60° C. After evaporation of thesolvent 0.38 g of the title compound are obtained as a white solid,which is directly used for the next reaction step. Elemental analysis %calculated C, H, N: 65.65, 11.02, 3.48 found: 66.04, 11.11, 3.40.

EXAMPLE A59 Preparation of Compound 159

2.27 g of compound 158 (6 mmol) in 25 ml water are mixed with 7.77 gtoluene-4-sulfonic acid sodium salt in 25 ml water. After 1 h stirringat room temperature 50 ml ether are added, the water phase isadditionally extracted twice with 50 ml ether, the organic phases arecombined, dried over MgSO₄ and the solvent is evaporated. 0.53 g of thetitle compound (86%) are obtained. Elemental analysis % calculated C, H,N, S: 70.54, 10.41, 2.84, 6.49%; found: 70.56, 10.74, 2.83, 5.93.

EXAMPLE A60 Preparation of Compound 160

To a solution of 2.31 g (10 mmol) α-bromomethyl-styrene in 10 ml ether,0.9 ml tetrahydrothiophen are added dropwise in 30 min. The titlecompound precipitates and is washed with ether.

Elemental analysis % calculated C, H: 54.74, 6.01; % found: 54.92, 5.96.

EXAMPLE A61 Preparation of Compound 161

Compound 160 of example 60 is dissolved in water together with KPF₆. Thetitle compound precipitates in a yield of 86%.

NMR (CDCl₃): 2.35 ppm (m, AA′BB′, 4H), 3.48 ppm (m, AA′BB′, 4H), 4.51ppm (s, 2H), 5.59 und 5.84 ppm (2s, olefinic, 2H), 7.41 ppm (m, 3H),7.56 ppm (m, 2H).

B) APPLICATION EXAMPLES Photochemical Polymerization of Methyl Acrylate20% in Ethyl Acetate

General Procedure

Polymerization without addition fragmentation agents. 90 g of a solutioncontaining 18 g methyl acrylate, 70.91 g ethyl acetate and 85.4 mg (0.42mmol) Irgacure 184 is irradiated under inert gas (argon) for 48 minutesat 25° C. with a 6 inch Fusion D-bulb in a 26 cm² reactor as describedin European Patent Application No. 97102677.8 setup A. The distancebetween the lamp and the reactor window in set-up (A) (no casserole) isfixed at 26 cm. The solution is stabilized with 25 ppm hydroxymethylhydroquinone. After isolation of the polymer the solvent is evaporatedto constant polymer weight.

Irgacure 184

The above procedure is carried out in the same manner, and variousaddition fragmentation agents are added in different amounts.

Mn and Mw are determined by gel permeation chromatography (GPC).

The results are given in Table 1

TABLE 1 Compound No. No. amount Mn PD B1 none 0 22100 2.9 B2 120 220 mg,0.2 mol % 13774 1.9 B3 120 540 mg, 0.5 mol % 8624 1.8 B4 120 1080 mg, 1mol % 6096 1.6 B5 119 189.2 mg, 0.2 mol % 13650 1.9 B6 119 473.1 mg, 0.5mol % 11254 1.8 B7 119 946.2 mg, 1 mol % 11550 1.8 B8 109 214.8 mg, 0.2mol % 16883 1.5 B9 109 536.9 mg, 0.5 mol % 8672 1.8 B10 109 1073.8 mg, 1mol % 6684 2.0 B11 111 184.6 mg, 0.2 mol % 13317 1.9 B12 111 461.4 mg,0.5 mol % 9981 1.9 B13 111 922.9 mg, 1 mol % 6386 1.7 B14 121 583 mg,0.5 mol % 8443 1.8, C_(x) = 1.24 B15 122 568.6 mg, 0.5 mol % 7439 1.9,C_(x) = 1.52 B16 123 723.3 mg, 0.5 mol % 11620 1.6, C_(x) = 0.68 B17 124480.3 mg, 0.5 mol % 7406 1.9, C_(x) = 1.53 B18 125 507.7 mg, 0.5 mol %7748 1.42, C_(x) = 1.42 PD = Polydispersity, C_(x) is transfercoefficient

C) APPLICATION EXAMPLES Thermal Polymerization of Methyl Acrylate

General Description of the Experiments.

Individual stock solutions are prepared as listed below. After additionof various amounts of addition fragmentation agent, the magneticallystirred solutions are heated under inert atmosphere for a given periodof time at a given temperature. After the reaction time the solutionsare cooled in an ice bath and 25 ppm of stabilizer (hydroquinone) areadded. The solvent is then removed under reduced pressure and thepolymer analyzed by GPC and NMR. To prevent any undesired reactions,solvents and monomers as well as reactants are purified by usualtechniques before use.

EXAMPLE C1

Stock solution: methyl acrylate 51.24 g, ethylacetate 193.57 g, AIBN182.9 mg Polymerization 16 hours at 60° C.

compound solution 119 Mn PD 38.02 g 0 122872 2.7 39.52 g 48.2 mg 178012.0 39.51 g 85.8 mg 11666 1.9 37.93 g 209.3 mg 6631 1.8 35.39 g 425 mg3741 1.8

EXAMPLE C2

Stock solution: methyl acrylate 60.98 g, ethyl acetate 60.52 g, AIBN113.5 mg Polymerization 16 hours at 60° C.

compound Solution 119 Mn PD 19.18 g 0 169647 4.6 19.34 g 50.8 mg 386242.1 19.52 g 113.4 mg 17676 2.2 19.34 g 258.4 mg 9062 2.1 19.13 g 556 mg5199 2.0

EXAMPLE C3

Stock solution: methyl acrylate 37.74 g, ethyl acetate 144 g, AIBN 137.3mg Polymerization 16 hours at 60° C.

compound Solution 120 Mn PD 30.48 g 0 205100 2.0 31.39 g 74.7 mg 641001.7   31 g 182.4 mg 23800 1.6 30.21 g 363.1 mg 9300 1.7 32.07 g 721.7 mg4900 1.5

EXAMPLE C4

Stock solution: methyl acrylate 61.96 g, ethyl acetate 60.32 g, AIBN115.5 mg Polymerization 16 hours at 60° C.

compound solution 120 Mn PD 20.21 g 0 200832 4.5 19.47 g 60.1 mg 1971362.9 19.44 g 120.8 mg 60216 2.9 19.16 g 300.7 mg 15450 2.4 20.55 g 603.5mg 8701 2.1

EXAMPLE C5

Stock solution: methyl acrylate 72.19 g, ethyl acetate 73.04 g, AIBN137.3 mg Polymerization 16 hours at 60° C.

Solution compound 120 Mn PD 40.27 g 0 219512 3.6 41.76 g 4.81 g 4036 1.3

EXAMPLE C6

Stock solution: methyl acrylate 50.92 g, ethyl acetate 192 g, AIBN 182.8mg Polymerization 16 hours at 60° C.

compound Solution 124 Mn PD 39.79 g 0 148969 2.6 41.03 g 45.2 mg 334452.4 40.41 g 88.3 mg 17232 2.1 40.17 g 209.9 mg 10197 2.0 40.66 g 444.1mg 6252 1.8

EXAMPLE C7

Stock solution: methyl acrylate 21.52 g, ethyl acetate 18.48 g, AIBN82.1 mg Polymerization 16 hours at 80° C.

solution compound 129 Mn PD 40.08 g 295.6 mg 55103 2.7

EXAMPLE C8

Stock solution: methyl acrylate 43.05 g, ethyl acetate 37.47 g, AIBN164.2 mg Polymerization 16 hours at 80° C.

solution compound 126 Mn PD 43 g 300 mg 33755 3.1

EXAMPLE C8

Stock solution: methyl acrylate 92.26 g, ethyl acetate 92.2 g, AIBN335.4 mg Polymerization 16 hours at 60° C.; C_(x) 1.17.

Solution compound 130 Mn PD 30.89 g  0 37167 4.2 30.76 g 515.9 mg 63022.1

EXAMPLE C9

Stock solution: methyl acrylate 43.05 g, ethyl acetate 36.92 g, AIBN164.2 mg Polymerization 16 hours at 80° C.

Solution compound 130 Mn PD 80 g 5.97 g 28488 2.4

EXAMPLE C10

Stock solution: methyl acrylate 17.22 g, ethyl acetate 0.00 g, AIBN 65.7mg Polymerization 16 hours at 80° C.

solution compound 128 Mn PD above 2.83 g 1058 2.3

EXAMPLE C11

Stock solution: methyl acrylate 43.05 g, ethyl acetate 31.88 g, AIBN164.2 mg Polymerization 16 hours at 80° C.

solution compound 131 Mn PD 75 g 2.5 g 3575 1.4

EXAMPLE C12

Stock solution: methyl acrylate 25.32 g, methyl ethyl ketone 95.45 g,AIBN 94.3 mg Polymerization 16 hours at 60° C.

compound solution 136 Mn PD 14.94 g — 30605 2.5 21.22 g 31 mg 18334 2.513.69 g 59.8 mg 4177 3.1  8.28 g 51 mg 2391 2.9 11.48 g 152.6 mg 15032.7

EXAMPLE C13

Stock solution: methyl acrylate 25.32 g, methyl ethyl ketone 95.45 g,AIBN 94.3 mg Polymerization 16 hours at 60° C.

compound solution 133 Mn PD 13.67 g — 28875 2.6 26.88 g 43.6 mg 170942.3 17.15 g 60 mg 5130 2.7 11.46 g 90.5 mg 2613 2.2 13.72 g 184.8 mg1662 2.2

EXAMPLE C14

Stock solution: methyl acrylate 16.11 g, methyl ethyl ketone 64.45 g,AIBN 61.3 mg Polymerization 16 hours at 60° C.; C_(x) 2.25.

solution weight compound 134 Mn PD 15.82 g — 23430 3.1  6.85 g 101.8 mg1717 2.1

EXAMPLE C15

Stock solution: methyl acrylate 16.11 g, methyl ethyl ketone 64.45 g,AIBN 61.3 mg Polymerization 16 hours at 60° C.; C_(x) 2.9

solution compound 135 Mn PD 15.82 g — 23430 3.2 25.76 g 393.1 mg 13732.8

EXAMPLE C16

Stock solution: methyl acrylate 61.77 g, ethyl acetate 60.82 g, AIBN118.6 mg Polymerization 1 hour at 60° C.

compound solution weight 110 Mn PD 19.95 g 0 178010 4.6 19.78 g 75.1 mg114303 5.8 20.30 g 127.2 mg 44125 4.0 20.26 g 294 mg 19322 3.1 20.31 g550 mg 8212 3.0

EXAMPLE C17

Stock solution: methyl acrylate 62.39 g, ethyl acetate 192 g, AIBN 183.9mg Polymerization 16 hour at 60° C.; C_(x) 0.95.

compound solution weight 109 Mn PD 40.88 g 0 158288 3.8 42.31 g 60.8 mgno GPC vergessen 37.92 g 140.9 mg 29291 2.4 41.12 g 189.3 mg 25141 2.940.32 g 341.2 mg 14401 2.9

EXAMPLE C18

Stock solution: methyl acrylate 40.13 g, ethyl acetate 39.79 g, AIBN 153mg Polymerization 16 hour at 60° C.; C_(x) 1.79.

solution compound 114 Mn PD 19.68 g  0 114505 5.1 19.43 g 242.6 mg 45791.8 20.26 g 382.6 mg 3527 1.7

EXAMPLE C19

Stock solution: methyl acrylate 10.76 g, ethyl acetate 8.85 g, AIBN164.2 mg Polymerization 16 hour at 60° C.

solution compound 114 Mn PD 19.68 g 1.75 g 1743 2.1

EXAMPLE C20

Stock solution: methyl acrylate 51.18 g, ethyl acetate 192 g, AIBN 184.9mg Polymerization 16 hour at 60° C.

compound solution 102 Mn PD 40.42 g 0 138960 3.0 39.66 g 51.5 mg 214631.9 40.48 g 144.8 mg 9143 1.9 39.39 g 213.2 mg 5390 1.6 38.03 g 381.1 mg3840 1.5

EXAMPLE C21

Stock solution: methyl acrylate 48.97 g, ethyl acetate 192 g, AIBN 183.5mg Polymerization 16 hours at 60° C.

compound solution 111 Mn PD 38.97 g 0 104769 3.4 40.19 g 68.7 mg 940662.8 40.12 g 134.4 mg 60637 2.6 40.80 g 280.9 mg 43733 2.6

EXAMPLE C22

Stock solution: methyl acrylate 48.66 g, ethyl acetate 191.74 g, AIBN181.4 mg Polymerization 16 hour at 60° C.

compound solution 146 Mn PD  40.0 g 0 114382 3.9 38.76 g 32.3 mg 468841.6 38.68 g 66.7 mg 20071 1.6 37.07 g 168.1 mg 9990 1.4

EXAMPLE C23

Stock solution: methyl acrylate 81.28 g, ethyl acetate 320.34 g, AIBN299.9 mg Polymerization 16 hour at 60° C.

solution compound quantity Mn PD C_(x) 39.22 g — 0 134884 3.4 39.25 gcompound 121 256 mg 10900 2 1.46 38.67 g compound 122 251 mg 12101 2.21.27 40.21 g compound 123 331.7 mg 20756 4.5 0.69 40.08 g compound 125233.6 mg 16169 2.4 0.92 39.59 g compound 119 218.8 mg 7494 1.9 2.0540.05 g compound 120 256.3 mg 12360 2.1 1.21 40.08 compound 124 226.3 mg10905 2.1 1.3

D) APPLICATION EXAMPLES Thermal Polymerization of Methyl Methacrylate

General Description of the Experiments.

The initial stock solution is separated in portions as listed below.After addition of various amounts of addition fragmentation agent, themagnetically stirred solutions are heated under inert atmosphere for agiven period of time at a given temperature. After the reaction time thesolutions are cooled in an ice bath and 25 ppm of stabilizer(hydroquinone) are added. The resulting reaction mixture is concentratedunder reduced pressure and the polymer analyzed by GPC and NMR. Toprevent any undesired reactions, solvents and monomers as well asreactants are purified by usual techniques before use.

EXAMPLE D1

Stock solution: methyl methacrylate 19.9 g, AIBN 33.2 mg; Polymerization1 hour 60° C.; C_(x) 0.73.

compound solution 119 Mn PD 3.63 g 0 248213 2.0 3.85 g 36.7 mg 39883 2.53.83 g 88.0 mg 17411 2.5 3.74 g 176.3 mg 11402 2.1

EXAMPLE D2

Stock solution: methyl methacrylate 60.5 g, AIBN 97 mg; Polymerization 1hour 100° C.; C_(x) 0.60.

compound Solution 119 Mn PD 10.42 g 0 146893 5.5 10.72 g 47.2 mg 553302.2 10.04 g 95.5 mg 28977 1.9 10.01 g 222.6 mg 19445 1.9 10.33 g 447.4mg 13683 1.9

EXAMPLE D3

Stock solution: methyl methacrylate 60.2 g, AIBN 99.5 mg; Polymerization1 hour 60° C.; C_(x) 0.27.

compound Solution 120 Mn PD 10.52 g 0 260800 1.7  9.86 g 102.6 mg 655001.8  9.80 g 256.5 mg 37661 1.5 10.15 g 517.3 mg 22343 1.7 10.28 g 1034mg 14900 1.6

EXAMPLE D4

Stock solution: methyl methacrylate 60.6 g, AIBN 98.8 mg; Polymerization1 hour 60° C.; C_(x) 0.33.

compound Solution 124 Mn PD 10.49 g 0 230733 1.6 10.19 g 103.7 mg 512992.1  9.95 g 234.7 mg 34422 1.8 10.33 g 456 mg 23615 1.7 10.07 g 918.7 mg12965 1.7

EXAMPLE D5

Stock solution: methyl methacrylate 61.1 g, AIBN 99.2 mg; Polymerization1 hour 60° C.

solution compound quantity Mn PD 10.56 g —  0 184982 2.4  9.86 gcompound 121 279.7 mg 8837 5.6  9.82 g compound 122 270.4 mg 25609 2.310.59 g compound 123 360.8 mg 32298 2.2 10.05 g compound 125 244.2 mg27537 2.2

EXAMPLE D6

Stock solution: methyl methacrylate 98.1 g, AIBN 170.4 mg;Polymerization 1 hour 60° C.

solution compound 124 Mn PD 10.02 g  0 169431 2.5  9.94 g 226.3 mg 191892.3

EXAMPLE D7

Stock solution: methyl methacrylate 70.1 g, AIBN 112.7 mg;Polymerization 1 hour 60° C.

solution compound 129 Mn PD 11.20 g  0 209423 2.1 10.25 g 295.6 mg173963 2.1

EXAMPLE D8

Stock solution: methyl methacrylate 70.1 g, AIBN 112.7 mg;Polymerization 1 hour 60° C.; C_(x) 0.14.

solution compound 126 Mn PD 11.20 g  0 209423 2.1 10.08 g 260.1 mg 539623.7

EXAMPLE D9

Stock solution: methyl methacrylate 70.1 g, AIBN 112.7 mg;Polymerization 1 hour 60° C.; C_(x) 0.46.

solution compound 130 Mn PD 11.2 g 0  209423 2.1 10.1 g 301 mg 19779 4.2

EXAMPLE D10

Stock solution: methyl methacrylate 50.4 g, AIBN 82.7 mg; Polymerization1 hour 60° C.; C_(x) 0.86.

solution compound 128 Mn PD  9.75 g 0  195555 2.0 10.59 g 360.5 mg 113711.9

EXAMPLE D11

Stock solution: methyl methacrylate 70.1 g, AIBN 112.7 mg;Polymerization 1 hour 60° C.; C_(x) 0.47.

solution compound 131 Mn PD 11.20 g 0  209423 2.1 10.15 g 547.6 mg 198212.2

EXAMPLE D12

Stock solution: methyl methacrylate 60.5 g, AIBN 100.1 mg;Polymerization 1 hour 60° C.; C_(x) 1.78.

solution compound 136 Mn PD 9.09 g 0 39478 4.4 10.6 g 142.5 mg 11130 2.9

EXAMPLE D13

Stock solution: methyl methacrylate 60.5 g, AIBN 100.1 mg;Polymerization 1 hour 60° C.; C_(x) 0.12.

compound solution 133 Mn PD  9.68 g 0 75937 2.6 10.60 g 161.4 mg 520812.6 11.29 g 405 mg 32355 2.5

EXAMPLE D14

Stock solution: methyl methacrylate 59.8 g, AIBN 99.9 mg; Polymerization1 hour 60° C.; C_(x) 0.24.

solution compound 134 Mn PD 9.09 g  0 39478 4.4 5.69 g 78.2 mg 27635 2.1

EXAMPLE D15

Stock solution: methyl methacrylate 59.8 g, AIBN 99.9 mg; Polymerization1 hour 60° C.; C_(x) 0.21.

solution compound 135 Mn PD  9.09 g  0 39478 4.4 10.26 g 173.4 mg 276662.4

EXAMPLE D16

Stock solution: methyl methacrylate 60.7 g, AIBN 101.9 mg;Polymerization 1 hour 60° C.; C_(x) 0.90.

solution compound 102 Mn PD 10.37 g  0 225272 2.1 12.53 g 121.5 mg 166292.3 9.13 g 208.3 mg 9211 2.0 9.42 g 325.3 mg 7613 2.0 9.51 g 944.3 mg3771 2.0

EXAMPLE D17

Stock solution: methyl methacrylate 61.0 g, AIBN 98.6 mg; Polymerization1 hour 60° C.

compound solution 112 Mn PD 9.85 g 0 193862 2.2 6.94 g 33.2 mg 78406 3.310.09 g 95.8 mg 51526 4.4 5.02 g 244.1 mg 45745 2.2

EXAMPLE D18

Stock solution: methyl methacrylate 60.2 g, AIBN 98.8 mg; Polymerization1 hour 60° C.; C_(x) 0.72.

compound solution 139 Mn PD 9.80 g 0 171059 2.2 6.07 g 29.50 mg 437233.2 11.35 g 123.7 mg 30824 3.1 10.35 g 287.1 mg 25155 3.6 7.12 g 339.5mg 11411 2.8

EXAMPLE D19

Stock solution: methyl methacrylate 59.3 g, AIBN 99.4 mg; Polymerization1 hour 60° C.; C_(x) 0.41.

compound solution 138 Mn PD 9.59 g 0 205250 2.3 9.91 g 21.8 mg 1085822.4 10.20 g 303 mg 28953 2.1 10.06 g 436.7 mg 21155 2.1

EXAMPLE D20

Stock solution: methyl methacrylate 62.3 g, AIBN 103.1 mg;Polymerization 1 hour 60° C.; C_(x) 0.58.

compound solution 103 Mn PD 9.22 g 0 215653 1.9 9.90 g 99.4 mg 28888 4.99.82 g 185.7 mg 16155 7.2 9.84 g 406 mg 11846 5.1

EXAMPLE D21

Stock solution: methyl methacrylate 60.8 g, AIBN 98.4 mg; Polymerization1 hour 60° C.

compound solution 143 Mn PD 9.59 g 0 249832 2.1 7.98 g 57.2 mg 26815 3.77.76 g 142.5 mg 10898 5.3

EXAMPLE D22

Stock solution: methyl acrylate 57.6 g, MEK 59.8 g, AIBN 101.0 mg;Polymerization 1 hour 60° C.; C_(x) 0.25.

compound solution 141 Mn PD 18.51 g 0 123834 2.1 19.44 g 34.7 mg 1300132.7 19.19 g 73.6 mg 43228 2.1 19.47 g 167.2 mg 51257 1.5 18.27 g 341.6mg 23847 1.5

EXAMPLE D23

Stock solution: methyl methacrylate 70.1 g, AIBN 112.7 mg;Polymerization 1 hour 60° C.

solution compound 145 Mn PD 11.2 g  0 209423 2.1 10.1 g 275 mg 75781 3.5

EXAMPLE D24

Stock solution: methyl methacrylate 62.3 g, AIBN 215.4 mg;Polymerization 1 hour 60° C.

compound solution 146 Mn PD  9.58 g 0 137396 2.1 10.13 g 33.1 mg 1137862.2 10.12 g 172.5 mg 73878 2.5 10.10 g 336.2 mg 40488 3.6

EXAMPLE D25

Stock solution: methyl methacrylate 60.0 g, AIBN 100 mg; Polymerization1 hour 60° C.

compound solution 148 Mn PD 9.73 g 0 179929 2.1 9.76 g 43.7 mg 85792 3.27.86 g 129 mg 22126 4.3 7.39 g 270.4 mg 16898 4.3

EXAMPLE D26

Stock solution: methyl methacrylate 60.0 g, AIBN 97.8 mg; Polymerization1 hour 60° C.

compound solution 110 Mn PD 10.54 g 0 195958 3.1  9.79 g 44.2 mg 1300132.7 10.34 g 93.1 mg 89698 2.6 10.30 g 182.3 mg 23198 4.9 10.94 g 672.2mg 14983 3.8

EXAMPLE D27

Stock solution: methyl methacrylate 60.0 g, AIBN 99.0 mg; Polymerization1 hour 60° C.; C_(x) 0.22.

solution compound 109 Mn PD  9.30 g  0 230238 1.8 10.55 g 105.3 mg125748 1.8 10.48 g 204.7 mg 81490 1.7 10.68 g 588.5 mg 47372 1.7 10.79 g962.0 mg 22797 1.7

EXAMPLE D28

Stock solution: methyl methacrylate 61.4 g, AIBN 99.4 mg; Polymerization1 hour 60° C.

solution compound 116 Mn PD 10.48 g  0 118726 3.9  9.88 g 134.5 mg 35531.6

EXAMPLE D29

Stock solution: methyl methacrylate 59.9 g, MEK 59.64 g, AIBN 97.8 mg;Polymerization 1 hour 60° C.

solution compound quantity Mn PD 21.64 g —  0 125296 2.3 19.82 gcompound 156 390.8 mg 56049 2.2 20.04 g compound 157 412.9 mg 49724 1.9

EXAMPLE D30

Stock solution: methyl methacrylate 59.8 g, AIBN 99.9 mg; Polymerization1 hour 60° C.; C_(x) 2.49.

compound solution 161 Mn PD 8.97 g 0 146007 2.5 9.68 g 34.5 mg 17881 3.09.97 g 66.4 mg 9077 3.0 10.01 g 336.1 mg 3529 2.2

E) APPLICATION EXAMPLES Thermal Polymerization of Styrene

General Description of the Experiments.

The initial stock solution is separated in portions as listed below.After addition of various amounts of addition fragmentation agent, themagnetically stirred solutions are heated under inert atmosphere for agiven period of time at a given temperature. After the reaction time thesolutions are cooled in an ice bath and 25 ppm of stabilizer(hydroquinone) are added. The resulting reaction mixture is concentratedunder reduced pressure and the polymer analyzed by GPC and NMR. Toprevent any undesired reactions, solvents and monomers as well asreactants are purified by usual techniques before use.

EXAMPLE E1

Stock solution: styrene 105.0 g, AIBN 159.6 mg; Polymerization 2 hours80° C.

solution compound quantity Mn PD 10.60 g —  0 57784 1.7 9.40 g compound121 267.3 mg 18915 2.0 9.84 g compound 122 267.6 mg 22027 2.1 9.91 gcompound 123 337.3 mg 25770 2.2 9.86 g compound 125 242.1 mg 18356 2.2

EXAMPLE E2

Stock solution: styrene 70.9 g, AIBN 108.7 mg; Polymerization 2 hours80° C.

solution compound 126 Mn PD  9.10 g  0 53221 1.8 10.29 g 245 mg 455511.9

EXAMPLE E3

Stock solution: styrene 70.9 g, AIBN 108.7 mg; Polymerization 2 hours80° C.

solution compound 130 Mn PD 9.10 g  0 53221 1.8 9.95 g 283.4 mg 337951.9

EXAMPLE E4

Stock solution: styrene 70.9 g, AIBN 108.7 mg; Polymerization 2 hours80° C.

solution compound 119 Mn PD  9.10 g  0 53221 1.8 10.25 g 437.4 mg 142592.1

EXAMPLE E5

Stock solution: styrene 70.9 g, AIBN 108.7 mg; Polymerization 2 hours80° C.

solution compound 128 Mn PD 9.10 g  0 53221 1.8 9.82 g 348.6 mg 128422.1

EXAMPLE E6

Stock solution: styrene 61.7 g, AIBN 95.2 mg; Polymerization 2 hours 80°C.

solution compound 136 Mn PD 9.03 g  0 49018 1.9 4.87 g 645 mg 16837 2.2

EXAMPLE E7

Stock solution: styrene 61.7 g, AIBN 95.2 mg; Polymerization 2 hours 80°C.

solution compound 133 Mn PD 9.03 g  0 49018 1.9 9.54 g 125.9 mg 329422.0

EXAMPLE E8

Stock solution: styrene 61.7 g, AIBN 87.5 mg; Polymerization 2 hours 80°C.

solution compound 134 Mn PD 9.95 g  0 54190 1.8 5.21 g 67.0 mg 22453 2.13.45 g 90.7 mg 19233 2.2

EXAMPLE E9

Stock solution: styrene 61.7 g, AIBN 87.5 mg; Polymerization 2 hours 80°C.

solution compound 135 Mn PD 9.95 g  0 54190 1.8 10.02 g 143.0 mg 193582.0 5.00 g 171.1 mg 15679 2.2

EXAMPLE E10

Stock solution: styrene 70.9 g, AIBN 108.7 mg; Polymerization 2 hours80° C.

solution compound 145 Mn PD  9.10 g  0 53221 1.8 10.18 g 275.9 mg 433282.0

EXAMPLE E11

Stock solution: styrene 59.7 g, AIBN 98 mg; Polymerization 2 hours 80°C.

compound solution 155 Mn PD 9.13 g 0 46783 1.9 9.96 g 54.4 mg 25429 2.39.50 g 110.5 mg 17226 2.6 9.47 g 256.6 mg 8086 3.5 9.77 g 551.5 mg 52933.4

EXAMPLE E12

Stock solution: styrene 60.9 g, heptane 60.9 g, AIBN 101.8 mg;Polymerization 2 hours 80° C.

solution compound 157 Mn PD 16.84 g  0 32501 1.7 19.39 g 223.4 mg 247701.7 21.24 g 422.8 mg 18650 1.7

EXAMPLE E13

Stock solution: styrene 65.2 g, AIBN 186 mg; Polymerization 2 hours 80°C.

compound solution 161 Mn PD 9.11 g 0 48277 1.9 10.26 g 39.6 mg 11105 3.99.68 g 69.2 mg 7745 4.0 10.08 g 168.0 mg 6857 4.1

F) APPLICATION EXAMPLES Thermal Polymerization of n-Butyl Acrylate

General Description of the Experiments.

The initial stock solution is separated in portions as listed below.After addition of various amounts of addition fragmentation agent, themagnetically stirred solutions are heated under inert atmosphere for agiven period of time at a given temperature. After the reaction time thesolutions are cooled in an ice bath and 25 ppm of stabilizer(hydroquinone) are added. The resulting reaction mixture is concentratedunder reduced pressure, further dried under high vacuum, and the polymeranalyzed by GPC and NMR. To prevent any undesired reactions, solventsand monomers as well as reactants are purified by usual techniquesbefore use.

EXAMPLE F1

Stock solution: n-butyl acrylate 53.97 g, toluene 125.9 g, AIBN 139.8mg; Polymerization 16 hours 60° C.; C_(x) 0.7.

compound solution 119 Mn PD 30.1 g 0 45943 3.8 29.7 g 63.8 mg 22308 2.530.1 g 159.1 mg 13680 2.2 29.8 g 319.2 mg 10113 2.0 30.0 g 636.9 mg 70262.0

EXAMPLE F2

Stock solution: n-butyl acrylate 102.1 g, toluene 238.2 g, AIBN 262.5mg; Polymerization 16 hours 60° C.; C_(x) 1.1.

compound solution 120 Mn PD 20.6 g 0 53095 3.9 20.5 g 49.9 mg 48003 2.520.0 g 122.2 mg 31013 2.3 20.0 g 243.7 mg 16210 2.2 19.8 g 484.1 mg 57352.2

EXAMPLE F3

Stock solution: n-butyl acrylate 54.0 g, toluene 126.0 g, AIBN 139.5 mg;Polymerization 16 hours 60° C.; C_(x) 1.1.

compound solution 128 Mn PD 29.6 g 0 37627 5.0 29.4 g 50.1 mg 21055 2.129.4 g 126.6 mg 12250 2.1 29.5 g 250.2 mg 7627 1.9 29.9 g 497.9 mg 50311.8

EXAMPLE F4

Stock solution: n-butyl acrylate 102.2 g, toluene 238.5 g, AIBN 261.6mg; Polymerization 16 hours 60° C.; C_(x) 2.8.

compound solution 150 Mn PD 30.5 g 0 49064 3.6 30.6 g 80.3 mg 19818 2.230.9 g 180.5 mg 7808 2.0 30.7 g 362.2 mg 4450 1.7

EXAMPLE F5

Stock solution: n-butyl acrylate 108.2 g, toluene 251.1 g, AIBN 278.4mg; Polymerization 16 hours 60° C.; C_(x) 1.8.

compound solution 151 Mn PD 30.6 g 0 47194 3.8 29.8 g 59.9 mg 19454 2.030.2 g 150.7 mg 8913 1.8 30.1 g 299.8 mg 5500 1.7 29.4 g 599.8 mg 31871.7

EXAMPLE F6

Stock solution: n-butyl acrylate 54.1 g, toluene 126.0 g, AIBN 141.6 mg;Polymerization 16 hours 60° C.; C_(x) 1.1.

compound solution 152 Mn PD 29.8 g 0 36417 4.6 30.3 g 73.2 mg 18243 2.230.5 g 159.3 mg 12324 2.2 30.3 g 344.3 mg 8557 2.0 30.8 g 655.4 mg 48222.1

EXAMPLE F7

Stock solution: n-butyl acrylate 54.2 g, toluene 126.4 g, AIBN 138.7 mg;Polymerization 16 hours 60° C.; C_(x) 2.1.

compound solution 153 Mn PD 30.0 g 0 64228 2.8 30.3 g 72.6 mg 21700 2.030.5 g 177.1 mg 9721 2.1 30.5 g 351.7 mg 5783 1.9

What is claimed is:
 1. A composition comprising a) at least one ethylenically unsaturated monomer or oligomer b) a radical initiator which forms a radical upon heating or upon irradiation with (UV) light from 305 nm to 450 nm and c) a compound of formula (Ia), (Ib) or (Ic)

 wherein Y is a group which activates the double bond towards Michael addition; X is halogen or the anion of a mono carboxylic acid from 1-12 carbon atoms, a monovalent oxo acid or complex acid; n is 0 or 1; R₁, R₂ R₃ are independently of each other hydrogen, unsubstituted C₁-C₁₈alkyl, C₃-C₁₈alkyl, interrupted by at least one nitrogen or oxygen atom, C₃-C₁₈alkenyl, C₃-C₁₈alkynyl, C₇-C₉phenylalkyl, C₃-C₁₂cycloalkyl or C₃-C₁₂cycloalkyl containing at least one nitrogen or oxygen atom; or C₁-C₁₈alkyl or C₃-C₁₈alkyl interrupted by at least one nitrogen or oxygen atom, C₃-C₁₈alkenyl, C₃-C₁₈alkynyl, C₇-C₉phenylalkyl, C₃-C₁₂cycloalkyl or C₃-C₁₂cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO₂, halogen, amino, hydroxy, cyano, carboxy, C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkylamino, C₁-C₄alkylamino, di(C₁-C₄alkyl)amino or by a group —O—C(O)—C₁-C₈alkyl; or phenyl, naphthyl, which are unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, halogen, cyano, hydroxy, carboxy, C₁-C₄alkylamino or di(C₁-C₄alkyl)amino; or R₁ and R₂, together with the linking hetero atom, form a C₃-C₁₂ heterocycloalkyl radical; or R₁ and R₂ form a group

 or R₁, R₂ and R₃ form a group


2. A composition according to claim 1, wherein Y is CN, C(O)halogen, COOR₄, C(O)R₄, CONR₅R₆, phenyl or naphthyl which are unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, halogen, nitro, cyano, hydroxy, carboxy, C₁-C₄alkylamino or di(C₁-C₄alkyl)amino; and R₄, R₅and R₆ are hydrogen or C₁-C₁₈alkyl.
 3. A composition according to claim 2, wherein Y is CN, COOR₄ or phenyl which is unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, halogen, cyano, hydroxy, carboxy, C₁-C₄alkylamino or di(C₁-C₄alkyl)amino; and R₄ is C₁-C₄alkyl.
 4. A composition according to claim 1, wherein X is Cl⁻, Br⁻, I⁻, ClO₄ ⁻, CF₃SO₃ ⁻, CH₃SO₃ ⁻, CF₃COO⁻, p-toluene sulfonate, HSO₄ ⁻, BF₄ ⁻, B(Phenyl)₄ ⁻, PF₆ ⁻, SbCl₆ ⁻, AsF₆ ⁻, SbF₆ ⁻ or a mono carboxylic acid from 1-12 carbon atoms.
 5. A composition according to claim 4, wherein X is Cl⁻, Br⁻, ClO₄ ⁻, CF₃SO₃ ⁻, CH₃SO₃ ⁻, CF₃COO⁻, BF₄ ⁻, or PF₆ ⁻.
 6. A composition according to claim 1, wherein n is
 0. 7. A composition according to claim 1, wherein R₁, R₂ and R₃ are independently of each other unsubstituted C₁-C₁₈alkyl, C₃-C₁₈alkyl interrupted by at least one nitrogen or oxygen atom, C₇-C₉phenylalkyl, C₃-C₁₂cycloalkyl or C₃-C₁₂cycloalkyl containing at least one nitrogen or oxygen atom; or C₁-C₁₈alkyl, C₃-C₁₈alkyl interrupted by at least one nitrogen or oxygen atom, C₇-C₉phenylalkyl, C₃-C₁₂cycloalkyl or C₃-C₁₂cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO₂, halogen, amino, hydroxy, cyano, carboxy, C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkylamino or di(C₁-C₄alkyl)amino; or phenyl, which is unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, halogen, cyano, hydroxy, carboxy, C₁-C₄alkylamino or di(C₁-C₄alkyl)amino; or R₁ and R₂, together with the linking hetero atom, form a C₄-C₇ heterocycloalkyl radical; or R₁ and R₂ form a group

or R₁, R₂ and R₃ form a group


8. A composition according to claim 7, wherein R₁, R₂ and R₃ independently of each other are unsubstituted C₁-C₁₂alkyl, C₃-C₁₂alkyl interrupted by at least one nitrogen or oxygen atom, benzyl or phenyl, which is unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, halogen, cyano, hydroxy, carboxy.
 9. A composition according to claim 1, wherein Y is CN, C(O)halogen, COOR₄, phenyl which is unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, halogen, cyano, hydroxy, carboxy, R₄, is C₁-C₈alkyl; X is Br⁻, ClO₄ ⁻, CF₃SO₃ ⁻, CH₃SO₃ ⁻, CF₃COO⁻, BF₄ ⁻ or PF₆ ⁻; and R₁, R₂ and R₃ independently of each other are unsubstituted C₁-C₁₂alkyl, C₃-C₁₂alkyl interrupted by at least one nitrogen or oxygen atom, benzyl or phenyl, which is unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, halogen, cyano, hydroxy, carboxy.
 10. A composition according to claim 1, wherein the ethylenically unsaturated monomer or oligomer is selected from the group consisting of ethylene, propylene, n-butylene, i-butylene, styrene, substituted styrene, conjugated dienes, acrolein, vinyl acetate, vinylpyrrolidone, vinylimidazole, maleic anhydride, (alkyl)acrylic acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylic esters, (meth)acrylonitriles, (alkyl)acrylamides, vinyl halides and vinylidene halides.
 11. A composition according to claim 10 wherein the ethylenically unsaturated monomer is ethylene, propylene, n-butylene, i-butylene, isoprene, 1,3-butadiene, α-C₅-C₁₈alkene, styrene, α-methyl styrene, p-methyl styrene or a compound of formula CH₂═C(R_(a))—(C═Z)—R_(b), wherein R_(a) is hydrogen or C₁-C₄alkyl, R_(b) is NH₂, O⁻(Me⁺), glycidyl, unsubstituted C₁-C₁₈alkoxy, C₂-C₁₀₀alkoxy interrupted by at least one N and/or O atom, or hydroxy-substituted C₁-C₁₈alkoxy, unsubstituted C₁-C₁₈alkylamino, di(C₁-C₁₈alkyl)amino, hydroxy-substituted C₁-C₁₈alkylamino or hydroxy-substituted di(C₁-C₁₈alkyl)amino, —O—CH₂—CH₂—N(CH₃)₂ or —O—CH₂—CH₂—N⁺H(CH₃)₂ An⁻; An⁻ is a anion of a monovalent organic or inorganic acid; Me is a monovalent metal atom or the ammonium ion, Z is oxygen or sulfur.
 12. A composition according to claim 11, wherein R_(a) is hydrogen or methyl, R_(b) is NH₂, gycidyl, unsubstituted or with hydroxy substituted C₁-C₄alkoxy, unsubstituted C₁-C₄alkylamino, di(C₁-C₄alkyl)amino, hydroxy-substituted C₁-C₄alkylamino or hydroxy-substituted di(C₁-C₄alkyl)amino; and Z is oxygen.
 13. A composition according to claim 11 in which the ethylenically unsaturated monomers are selected from the group consisting of styrene, methylacrylate, ethylacrylate, butylacrylate, isobutylacrylate, tert. butylacrylate, hydroxyethylacrylate, hydroxypropylacrylate, dimethylaminoethylacrylate, glycidylacrylates, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate, glycidyl(meth)acrylates, acrylonitrile, acrylamide, methacrylamide and dimethylaminopropyl-methacrylamide.
 14. A process for preparing an oligomer, a cooligomer, a polymer or a copolymer (block or random) by free radical polymerization of a) at least one ethylenically unsaturated monomer or oligomer, which comprises (co)polymerizing the monomer or monomers/oligomers in the presence of b) a radical initiator which forms a radical upon heating or upon irradiation with (UV) light from 305 nm to 450 nm and c) a compound of formula (Ia), (Ib) or (Ic) according to claim 1 by subjecting the mixture to heat or electromagnetic radiation in the wavelength range from 305 nm to 450 nm.
 15. A process according to claim 14, wherein the radical initiator b) is present in an amount of 0.01 to 5 mol % based on the monomer or monomer mixture.
 16. A process according to claim 14, wherein the compound of formula (Ia), (Ib) or (Ic) is present in an amount of 0.01 to 10 mol % based on the monomer or monomer mixture.
 17. A polymer or copolymer prepared by the process of claim 14 containing a vinyl- or 1,3 dienyl group at one end of the molecule.
 18. A compound of formula (Ia), (Ib) or (Ic)

wherein Y is CN, C(O)halogen, COOR₄, C(O)R₄, CONR₅R₆, phenyl or naphthyl which are unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, halogen, nitro, cyano, hydroxy, carboxy, C₁-C₄alkylamino or di(C₁-C₄alkyl)amino; and R₄, R₅ and R₆ are hydrogen or C₁-C₁₈alkyl; X is Cl⁻, Br⁻, —I⁻, ClO₄ ⁻, CF₃SO₃ ⁻, CH₃SO₃ ⁻, CF₃COO⁻, p-toluene sulfonate, HSO₄ ⁻, BF₄ ⁻, B(Phenyl)₄ ⁻, PF₆ ⁻, SbCl₆ ⁻, AsF₆ ⁻, SbF₆ ⁻ or a mono carboxylic acid from 1-12 carbon atoms; n is 0 or 1; R₁, R₂ R₃ are independently of each other hydrogen, unsubstituted C₁-C₁₈alkyl, C₃-C₁₈alkyl, interrupted by at least one nitrogen or oxygen atom, C₃-C₁₈alkenyl, C₃-C₁₈alkynyl, C₇-C₉phenylalkyl, C₃-C₁₂cycloalkyl or C₃-C₁₂cycloalkyl containing at least one nitrogen or oxygen atom; or C₁-C₁₈alkyl, C₃-C₁₈alkyl, interrupted by at least one nitrogen or oxygen atom, C₃-C₁₈alkenyl, C₃-C₁₈alkynyl, C₇-C₉phenylalkyl, C₃-C₁₂cycloalkyl or C₃-C₁₂cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO₂, halogen, amino, hydroxy, cyano, carboxy, C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkylamino, di(C₁-C₄alkyl)amino or by a group —O—C(O)—C₁-C₁₈alkyl; or phenyl, naphthyl, which are unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, halogen, cyano, hydroxy, carboxy, C₁-C₄alkylamino or di(C₁-C₄alkyl)amino; or R₁ and R₂, together with the linking hetero atom, form a C₃-C₁₂heterocycloalkyl radical; R₁₀ and R₂₀ are independently of each other C₃-C₁₈alkyl which is unsubstituted or substituted by NO₂, halogen, amino, hydroxy, cyano, carboxy, C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkylamino or di(C₁-C₄alkyl)amino; and R₃₀ is hydrogen or methyl.
 19. A compound of formula (Ia) according to claim 18, wherein Y is phenyl, CN or COOR₄ and R₄ is C₁-C₄alkyl.
 20. A compound of formula (Ia) according to claim 18, wherein X is Cl or Br. 